EP0213567B1 - Process for applying phosphate coatings - Google Patents
Process for applying phosphate coatings Download PDFInfo
- Publication number
- EP0213567B1 EP0213567B1 EP86111618A EP86111618A EP0213567B1 EP 0213567 B1 EP0213567 B1 EP 0213567B1 EP 86111618 A EP86111618 A EP 86111618A EP 86111618 A EP86111618 A EP 86111618A EP 0213567 B1 EP0213567 B1 EP 0213567B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- ions
- weight
- fluoride
- chloride
- phosphate
- 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 - Lifetime
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 17
- 238000000576 coating method Methods 0.000 title claims abstract description 13
- 229910019142 PO4 Inorganic materials 0.000 title claims description 18
- 239000010452 phosphate Substances 0.000 title claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 33
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 32
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011701 zinc Substances 0.000 claims abstract description 14
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 14
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- -1 fluoride ions Chemical class 0.000 claims abstract description 7
- 229910001437 manganese ion Inorganic materials 0.000 claims abstract description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims description 26
- 239000002184 metal Substances 0.000 claims description 26
- 229910002651 NO3 Inorganic materials 0.000 claims description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 7
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 3
- 229910001453 nickel ion Inorganic materials 0.000 claims description 3
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims 1
- 229910001447 ferric ion Inorganic materials 0.000 claims 1
- 150000002500 ions Chemical class 0.000 abstract description 7
- 239000013078 crystal Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 abstract 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 abstract 1
- 230000002159 abnormal effect Effects 0.000 abstract 1
- 239000003929 acidic solution Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 229940085991 phosphate ion Drugs 0.000 abstract 1
- 235000021317 phosphate Nutrition 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- 101100117236 Drosophila melanogaster speck gene Proteins 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 229940104869 fluorosilicate Drugs 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920001665 Poly-4-vinylphenol Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 229910000165 zinc phosphate Inorganic materials 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 238000005246 galvanizing Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- JTDPJYXDDYUJBS-UHFFFAOYSA-N quinoline-2-carbohydrazide Chemical compound C1=CC=CC2=NC(C(=O)NN)=CC=C21 JTDPJYXDDYUJBS-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- 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 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
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
- C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
- C23C22/362—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also zinc cations
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
- C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
Definitions
- the invention relates to a method for applying phosphate coatings on metal surfaces consisting entirely or partially of zinc or zinc alloys by means of acidic aqueous phosphating solutions which contain zinc and / or manganese ions as well as phosphate ions and fluoride ions.
- phosphate coatings to metal surfaces by bringing them into contact with phosphating solutions which contain phosphate ions, zinc and / or manganese ions and optionally additionally nickel, cobalt and / or copper ions, nitrate and / or nitrite, fluoroborate and / or Contains fluorosilicate.
- the metal surfaces treated according to the process mentioned above are often not of the desired quality.
- the sheets show considerable roughness after they have been painted.
- the gloss of the paint layer and its adhesion to the metal surface does not meet the highest demands.
- Another problem that occurs particularly on galvanized surfaces or surface areas is the so-called speck formation. These are white structures resulting from uncontrolled crystal growth in small to pinhead-sized areas, primarily from zinc phosphate of different sizes with a diameter of 50 to 150 ⁇ rn and a height of 100 to 400 J.Lm, which ultimately lead to a faulty rough surface.
- the object of the invention is to provide a method for producing phosphate coatings on metal surfaces consisting entirely or partially of zinc or zinc alloys, which reliably and regularly eliminates the aforementioned problems of speck formation, yet is simple and economical to carry out.
- a preferred embodiment of the invention provides for the metal surfaces to be brought into contact with a phosphating solution which contains fluoride in the form of complex fluoride, in particular in the form of fluorosilicate. This applies in particular if the zinc surface was formed by hot-dip galvanizing.
- fluorosilicate other complex fluorides are also suitable, albeit with a reduced effect.
- the fluoride content should be increased with an increasing proportion of the zinc surface.
- a concentration of 0.05 to 0.2% by weight, in particular 0.075 to 0.2% by weight should be selected.
- the fluoride concentration can be adjusted with the aid of a fluoride-sensitive electrode - if necessary after making calibration curves.
- a further preferred embodiment of the invention provides for the metal surfaces to be brought into contact with a phosphating solution which contains 0.5 to 2.5% by weight, preferably 0.5 to 2.0% by weight, of phosphate.
- the phosphating solutions usually contain one or more accelerators. It is particularly advantageous if the metal surface is brought into contact with a phosphating solution which additionally contains nitrate, preferably in amounts of 0.025 to 2.0% by weight, in particular 0.05 to 1.0% by weight. When dosing it must be taken into account that nitrate can form during the formation of the coating, e.g. B. when nitrite is used as an accelerator. Controlled addition of nitrate is preferred.
- Zinc and / or manganese as well as phosphate and optionally nitrate are introduced into the phosphating solution in a manner known per se.
- a further advantageous embodiment of the invention provides for the metal surfaces to be brought into contact with a phosphating solution which additionally contains cobalt and / or nickel ions, preferably in amounts of 0.01 to 1.0% by weight.
- a phosphating solution which additionally contains cobalt and / or nickel ions, preferably in amounts of 0.01 to 1.0% by weight.
- These ions are expediently introduced in the form of their sulfates, phosphates, carbonates or nitrates, but in particular in the form of the carbonates.
- the phosphating solutions used in the process according to the invention can contain iron (III) ions.
- the iron ions can be introduced into the phosphating solution in the form of salts; if the treated metal surface is partly made of steel, they can also get into the solution from the metal surface by pickling. If the addition is via a salt, its anion should not impair the effectiveness of the phosphating solution.
- Suitable salts are acid phosphates, nitrate, fluoride or fluoroborate. If all or part of the iron comes from the metal surface, it should be converted into the trivalent state by suitable oxidizing agents, such as hydrogen peroxide, permanganate or nitrite.
- the concentration of iron III ions should be at least 0.0015% by weight and can reach the saturation limit.
- the preference for the content of iron III ions consists in particular in a reduction in the layer weight of the phosphate coating over a wide pH range of the phosphating solution.
- the content of iron III ions is characterized by the formation of particularly adhesive phosphate coatings.
- the contact of the metal surface with the phosphating solution can take place by conventional techniques, in particular by spraying, roller application, spraying on previously heated surfaces or by immersing the part of the metal surface to be coated in the phosphating solution.
- the temperature of the phosphating solution can be between 43.3 ° C and the boiling point of the solution. However, temperatures in the range of 54.4 to 82.2 ° C are particularly useful, with the best results when spraying, roller application and spraying on preheated metal surfaces at 65.5 ° C and when immersing between 43.3 and 54.4 ° C lie.
- a rinse solution which may additionally contain chromium III ions can be used for this purpose.
- a chromic acid solution which may additionally contain chromium III ions can be used for this purpose.
- Another group of suitable rinse solutions contains poly-4-vinylphenol or the reaction product of poly-4-vinylphenol with an aldehyde or a ketone (US Pat. Nos. 3,975,214, 4376000, 4457790, 4,039,353, 4433015).
- another advantageous embodiment of the invention provides for the metal surfaces to be brought into contact with a phosphating solution in which the weight ratio of fluoride to chloride is at least 10 : 1, preferably at least 14: 1.
- the phosphating solution has a certain buffering effect against new and possibly unexpected chloride inputs.
- the fluoride concentration to be set does not have to be selected to be excessively high, it is advisable to ensure that an unnecessarily high chloride input is avoided either when preparing the phosphating solution itself or by carrying in solution residues from the pretreatment stage. This means that care should already be taken to ensure that the chloride levels in the baths of the Pretreatment level should be kept as low as possible.
- the chloride content of these solutions should be below 100 ppm if possible.
- the activating agents used in the activating pre-rinse are generally obtained by neutralizing titanyl sulfate with sodium hydroxide solution and subsequent treatment with phosphoric acid.
- the activating pre-rinse solutions often contain more than 400 ppm chloride.
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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)
- Materials For Medical Uses (AREA)
Abstract
Description
Die Erfindung betrifft ein Verfahren zum Aufbringen von Phosphatüberzügen auf ganz oder teilweise aus Zink oder Zinklegierungen bestehende Metalloberflächen mittels saurer wäßriger Phosphatierungslösungen, die Zink- und/oder Manganionen sowie Phosphationen und Fluoridionen enthalten.The invention relates to a method for applying phosphate coatings on metal surfaces consisting entirely or partially of zinc or zinc alloys by means of acidic aqueous phosphating solutions which contain zinc and / or manganese ions as well as phosphate ions and fluoride ions.
Es ist bekannt, auf Metalloberflächen Phosphatüberzüge aufzubringen, indem man sie mit Phosphatierungslösungen in Kontakt bringt, die Phosphationen, Zink- und/oder Manganionen sowie gegebenenfalls zusätzlich Nickel-, Kobalt- und/oder Kupferionen, Nitrat und/oder Nitrit, Fluoroborat und/oder Fluorosilikat, enthält.It is known to apply phosphate coatings to metal surfaces by bringing them into contact with phosphating solutions which contain phosphate ions, zinc and / or manganese ions and optionally additionally nickel, cobalt and / or copper ions, nitrate and / or nitrite, fluoroborate and / or Contains fluorosilicate.
In jüngerer Zeit erlangt die Erzeugung von Phosphatüberzügen auf ganz oder teilweise verzinkten Stahloberflächen zunehmend an Bedeutung. Der dabei angewendete Verfahrensgang besteht üblicherweise aus den Stufen
- 1. Vorbehandlung, z. B. durch Reinigung, Spülung und Aktivierung,
- 2. die eigentliche Phosphatierung,
- 3. die Nachbehandlung, z. B. durch Wasserspülung und Applikation von Nachspüllösungen.
- 1. Pretreatment, e.g. B. by cleaning, rinsing and activation,
- 2. the actual phosphating,
- 3. the after-treatment, e.g. B. by water rinsing and application of rinse solutions.
Die nach dem vorstehend genannten Verfahrensgang behandelten Metalloberflächen sind jedoch häufig nicht von der erwünschten Qualität. Beispielsweise zeigen die Bleche nach ihrer Lackierung eine beträchtliche Rauhigkeit. Auch genügt mitunter der Glanz der Lackschicht und deren Haftung auf der Metalloberfläche nicht höchsten Ansprüchen. Ein anderes Problem, das besonders auf verzinkten Oberflächen oder Oberflächenbereichen auftritt, besteht in der sogenannten Stippenbildung. Hierbei handelt es sich um durch unkontrolliertes Kristallwachstum an kleinen bis stecknadelkopfgroßen Stellen entstehende weiße Gebilde, vornehmlich aus Zinkphosphat unterschiedlicher Größe mit einem Durchmesser von 50 bis 150 µrn und einer Höhe von 100 bis 400 J.Lm, die letztlich zu einer fehlerhaften rauhen Oberfläche führen.However, the metal surfaces treated according to the process mentioned above are often not of the desired quality. For example, the sheets show considerable roughness after they have been painted. Sometimes the gloss of the paint layer and its adhesion to the metal surface does not meet the highest demands. Another problem that occurs particularly on galvanized surfaces or surface areas is the so-called speck formation. These are white structures resulting from uncontrolled crystal growth in small to pinhead-sized areas, primarily from zinc phosphate of different sizes with a diameter of 50 to 150 µrn and a height of 100 to 400 J.Lm, which ultimately lead to a faulty rough surface.
Diese Stippen sind, sofern die Abmessungen im oberen Bereich liegen, bereits mit bloßem Auge wahrnehmbar, sofern die Abmessungen im unteren Bereich liegen, nur bei Vergrößerung sichtbar. Nach der Lackierbehandlung lassen sich jedoch in beiden Fällen Mängel beobachten, gleichgültig, ob der Lack durch Spritzverfahren oder eine Elektrotauchbehandlung aufgebracht worden ist.If the dimensions are in the upper area, these specks can already be seen with the naked eye, provided the dimensions are in the lower area, only when magnified. After the painting treatment, however, defects can be observed in both cases, regardless of whether the paint has been applied by spraying or an electro-dip treatment.
Es sind bereits zahlreiche Versuche unternommen worden, dieses speziell bei der Phosphatierung von Zinkoberflächen, insbesondere verzinkten Oberflächen, auftretende Problem zu lösen. Hierbei richtete sich die Aufmerksamkeit auf die Phosphatierbehandlung selbst (US-PSs2835617 und 3 240 633). In beiden Fällen wird vorgeschlagen, durch Verwendung von Fluorid in Phosphatierungsbädem die Stippenbildung zu vermeiden. Es wurde jedoch festgestellt, daß diese Vorschläge keineswegs immer zum Ziel führen, insbesondere wenn aus Gründen der Wirtschaftlichkeit und des Umweltschutzes möglichst geringe Fluoridmengen eingesetzt werden.Numerous attempts have already been made to solve this problem, which occurs particularly in the phosphating of zinc surfaces, in particular galvanized surfaces. Here, attention was paid to the phosphating treatment itself (US Pat. Nos. 2,835,617 and 3,240,633). In both cases it is proposed to avoid speck formation by using fluoride in phosphating baths. However, it was found that these suggestions do not always lead to the goal, especially if the lowest possible amounts of fluoride are used for reasons of economy and environmental protection.
Aufgabe der Erfindung ist es, ein Verfahren zur Erzeugung von Phosphatüberzügen auf ganz oder teilweise aus Zink oder Zinklegierungen bestehende Metalloberflächen bereitzustellen, das die vorgenannten Probleme der Stippenbildung mit Sicherheit und regelmäßig beseitigt, dennoch einfach und wirtschaftlich in der Durchführung ist.The object of the invention is to provide a method for producing phosphate coatings on metal surfaces consisting entirely or partially of zinc or zinc alloys, which reliably and regularly eliminates the aforementioned problems of speck formation, yet is simple and economical to carry out.
Die Aufgabe wird gelöst, indem das Verfahren der eingangs genannten Art entsprechend der Erfindung derart ausgestaltet wird, daß man die Metalloberflächen mit einer Phosphatierungslösung in Kontakt bringt, die
- 0,5 bis 4 Gew.-% Phosphationen,
- 0,01 bis 1 Gew.-% Fluoridion (berechnet als F)
- 0.5 to 4% by weight of phosphate ions,
- 0.01 to 1 wt% fluoride ion (calculated as F)
Bei der Auseinandersetzung mit dem Problem wurde festgestellt, daß die Gegenwart von Chloridionen für die Stippenbildung verantwortlich ist. Sie läßt sich entsprechend den oben zitierten Vorschlägen so lange in Grenzen halten, wie die vorhandene Chloridkonzentration gering ist; mit steigender Konzentration tritt sie jedoch wieder auf. Hierbei ist zu berücksichtigen, daß der Eintrag von Chloridionen in die Phosphatierungslösung keineswegs beabsichtigt erfolgt, sich aber aus vielerlei Gründen häufig nicht oder nur schwer vermeiden läßt. Es ist nämlich in großtechnischem Einsatz praktisch unmöglich, sämtliches Chlorid zu entfernen bzw. fernzuhalten. Beispielsweise gelangt durch produktionsbedingte Verunreinigung stets Chlorid in das Phosphatierungsbad. Auch läßt sich bei Verwendung von Chlorat als Beschleuniger schon wegen des Chemismus die Entstehung von Chlorid nicht vermeiden.When dealing with the problem, it was found that the presence of chloride ions is responsible for the formation of specks. According to the proposals cited above, it can be kept within limits as long as the chloride concentration present is low; however, with increasing concentration, it reappears. It should be taken into account here that the introduction of chloride ions into the phosphating solution is by no means intentional, but it is often difficult or impossible to avoid for many reasons. It is in fact practically impossible in large-scale use to remove or keep all the chloride away. For example, chloride always gets into the phosphating bath due to production-related contamination. Even when using chlorate as an accelerator, the formation of chloride cannot be avoided simply because of the chemistry.
Es ist unstrittig, daß der effektiven Chloridkonzentration in der Phosphatierungslösung jedenfalls keine besondere Beachtung geschenkt wurde. Erst im Zusammenhang mit der Konzeption der vorliegenden Erfindung wurde erkannt, daß hinsichtlich Chlorid- und Fluoridkonzentration gegenseitige Abhängigkeiten bestehen bzw. daß man den nachteiligen Effekt, der mit steigender Chloridkonzentration auftreten würde, vermeiden kann, wenn man gleichzeitig die Fluoridkonzentration entsprechend der vorstehend genannten Lehre anhebt.It is indisputable that the effective chloride concentration in the phosphating solution was in any case not given special attention. Only in connection with the conception of the present invention was it recognized that there are interdependencies with regard to chloride and fluoride concentration or that the disadvantageous effect which would occur with increasing chloride concentration can be avoided by simultaneously increasing the fluoride concentration in accordance with the above-mentioned teaching .
Grundsätzlich kann die Einstellung des Gewichtsverhältnisses von Fluorid zu Chlorid mit Hilfe von einfachem Fluorid, insbesondere mit Flußsäure, vorgenommen werden. Es hat sich jedoch gezeigt, daß der Effekt besonders groß ist, wenn das Fluorid in Form von komplexem Fluorid zugegeben wird. Demzufolge sieht eine bevorzugte Ausgestaltung der Erfindung vor, die Metalloberflächen mit einer Phosphatierungslösung in Kontakt zu bringen, die Fluorid in Form von komplexem Fluorid, und zwar insbesondere in Form von Fluorosilikat, enthält. Dies gilt in besonderem Maße, wenn die Zinkoberfläche durch Feuerverzinkung gebildet worden ist. Wenn auch mit verringerter Wirkung, sind neben Fluorosilikat auch andere komplexe Fluoride geeignet.Basically, you can adjust the weight ratio of fluoride to chloride with the help of simple fluoride, especially with hydrofluoric acid. However, it has been shown that the effect is particularly great when the fluoride is added in the form of complex fluoride. Accordingly, a preferred embodiment of the invention provides for the metal surfaces to be brought into contact with a phosphating solution which contains fluoride in the form of complex fluoride, in particular in the form of fluorosilicate. This applies in particular if the zinc surface was formed by hot-dip galvanizing. In addition to fluorosilicate, other complex fluorides are also suitable, albeit with a reduced effect.
Bei der Bemessung des Fluorids ist weiterhin zu beachten, daß mit steigenden Anteil der Zinkoberfläche der Fluoridgehalt angehoben werden sollte. Beispielsweise sollte bei einem Zinkanteil von mehr als 50 % an der Gesamtoberfläche eine Konzentration von 0,05 bis 0,2 Gew.-%, insbesondere von 0,075 bis 0,2 Gew.-%, gewählt werden. Die Fluoridkonzentration kann unter Zuhilfenahme einer fluoridsensitiven Elektrode - gegebenenfalls nach Anfertigung von Eichkurven - eingestellt werden.When dimensioning the fluoride, it should also be noted that the fluoride content should be increased with an increasing proportion of the zinc surface. For example, with a zinc content of more than 50% of the total surface, a concentration of 0.05 to 0.2% by weight, in particular 0.075 to 0.2% by weight, should be selected. The fluoride concentration can be adjusted with the aid of a fluoride-sensitive electrode - if necessary after making calibration curves.
Besonders vorteilhaft ist es, den Gehalt der Phosphatierungslösung an Zink- und/oder Manganionen derart zu bemessen, daß etwa mit dem vorhandenen Phosphat Dihydrogenphosphat gebildet wird.It is particularly advantageous to measure the content of zinc and / or manganese ions in the phosphating solution such that dihydrogen phosphate is formed, for example, with the phosphate present.
Eine weitere bevorzugte Ausgestaltung der Erfindung sieht vor, die Metalloberflächen mit einer Phosphatierungslösung in Kontakt zu bringen, die 0,5 bis 2,5 Gew.-%, vorzugsweise 0,5 bis 2,0 Gew.-%, Phosphat enthält.A further preferred embodiment of the invention provides for the metal surfaces to be brought into contact with a phosphating solution which contains 0.5 to 2.5% by weight, preferably 0.5 to 2.0% by weight, of phosphate.
Zur Beschleunigung der Ausbildung des Phosphatüberzuges enthalten die Phosphatierungslösungen üblicherweise einen oder mehrere Beschleuniger. Besonders vorteilhaft ist es, wenn die Metalloberfläche mit einer Phosphatierungslösung in Kontakt gebracht wird, die zusätzlich Nitrat, vorzugsweise in Mengen von 0,025 bis 2,0 Gew.-%, insbesondere von 0,05 bis 1,0 Gew.-%, enthält. Bei der Dosierung ist zu berücksichtigen, daß Nitrat bei der Überzugsbildung entstehen kann, z. B. wenn Nitrit als Beschleuniger verwendet wird. Der kontrollierten Nitratzugabe wird jedoch der Vorzug gegeben.To accelerate the formation of the phosphate coating, the phosphating solutions usually contain one or more accelerators. It is particularly advantageous if the metal surface is brought into contact with a phosphating solution which additionally contains nitrate, preferably in amounts of 0.025 to 2.0% by weight, in particular 0.05 to 1.0% by weight. When dosing it must be taken into account that nitrate can form during the formation of the coating, e.g. B. when nitrite is used as an accelerator. Controlled addition of nitrate is preferred.
Die Einbringung von Zink und/oder Mangan sowie von Phosphat und gegebenenfalls Nitrat in die Phosphatierungslösung geschieht in an sich bekannter Weise.Zinc and / or manganese as well as phosphate and optionally nitrate are introduced into the phosphating solution in a manner known per se.
Eine weitere vorteilhafte Ausführungsform der Erfindung sieht vor, die Metalloberflächen mit einer Phosphatierungslösung in Kontakt zu bringen, die zusätzlich Kobalt- und/oder Nickelionen, vorzugsweise in Mengen von 0,01 bis 1,0 Gew.-%, enthält. Diese Ionen werden zweckmäßigerweise in Form ihrer Sulfate, Phosphate, Karbonate oder Nitrate, insbesondere aber in Form der Karbonate eingebracht.A further advantageous embodiment of the invention provides for the metal surfaces to be brought into contact with a phosphating solution which additionally contains cobalt and / or nickel ions, preferably in amounts of 0.01 to 1.0% by weight. These ions are expediently introduced in the form of their sulfates, phosphates, carbonates or nitrates, but in particular in the form of the carbonates.
Schließlich können die im erfindungsgemäßen Verfahren eingesetzten Phosphatierungslösungen Eisen-III-Ionen enthalten. Die Eisen-Ionen können in die Phosphatierungslösung in Form von Salzen eingebracht werden ; sie können, sofern die behandelte Metalloberfläche auch teilweise aus Stahl besteht, auch durch den Beizangriff von der Metalloberfläche in die Lösung gelangen. Sofern die Zugabe über ein Salz erfolgt, sollte dessen Anion die Wirksamkeit der Phosphatierungslösung nicht beeinträchtigen. Geeignete Salze sind saure Phosphate, Nitrat, Fluorid oder Fluoroborat. Wenn das Eisen ganz oder teilweise aus der Metalloberfläche stammt, sollte es durch geeignete Oxidationsmittel, wie Wasserstoffperoxid, Permanganat oder Nitrit, in den dreiwertigen Zustand überführt werden. Die Konzentration an Eisen-III-Ionen sollte wenigstens 0,0015 Gew.-% betragen und kann bis zur Sättigungsgrenze reichen.Finally, the phosphating solutions used in the process according to the invention can contain iron (III) ions. The iron ions can be introduced into the phosphating solution in the form of salts; if the treated metal surface is partly made of steel, they can also get into the solution from the metal surface by pickling. If the addition is via a salt, its anion should not impair the effectiveness of the phosphating solution. Suitable salts are acid phosphates, nitrate, fluoride or fluoroborate. If all or part of the iron comes from the metal surface, it should be converted into the trivalent state by suitable oxidizing agents, such as hydrogen peroxide, permanganate or nitrite. The concentration of iron III ions should be at least 0.0015% by weight and can reach the saturation limit.
Der Vorzug des Gehaltes an Eisen-III-Ionen besteht insbesondere in einer Reduktion des Schichtgewichtes des Phosphatüberzuges über einen weiten pH-Bereich der Phosphatierungslösung hinweg. Bei . Phosphatierungslösungen mit einer Gesamtsäurepunktzahl von 10 bis 110 zeichnet sich der Gehalt an Eisen-III-Ionen durch die Entstehung besonders haftfester Phosphatüberzüge aus.The preference for the content of iron III ions consists in particular in a reduction in the layer weight of the phosphate coating over a wide pH range of the phosphating solution. At. Phosphating solutions with a total acid number of 10 to 110, the content of iron III ions is characterized by the formation of particularly adhesive phosphate coatings.
Der Kontakt der Metallöberfläche mit der Phosphatierungslösung kann durch übliche Techniken, insbesondere durch Spritzen, Rollenauftrag, Sprühen auf zuvor erhitzte Oberflächen oder durch Tauchen des zu beschichtenden Teils der Metalloberfläche in die Phosphatierungslösung erfolgen. Die Temperatur der Phosphatierungslösung kann zwischen 43,3 °C und dem Siedepunkt der Lösung liegen. Besonders zweckmäßig sind jedoch Temperaturen im Bereich von 54,4 bis 82,2 °C, wobei die besten Ergebnisse beim Spritzen, Rollenauftrag und Sprühen auf vorerhitzte Metalloberflächen bei 65,5 °C und beim Tauchen zwischen 43,3 und 54,4 °C liegen.The contact of the metal surface with the phosphating solution can take place by conventional techniques, in particular by spraying, roller application, spraying on previously heated surfaces or by immersing the part of the metal surface to be coated in the phosphating solution. The temperature of the phosphating solution can be between 43.3 ° C and the boiling point of the solution. However, temperatures in the range of 54.4 to 82.2 ° C are particularly useful, with the best results when spraying, roller application and spraying on preheated metal surfaces at 65.5 ° C and when immersing between 43.3 and 54.4 ° C lie.
Im Anschluß an die Erzeugung des Phosphatüberzuges ist es - insbesondere wenn eine anschließende Lackierung beabsichtigt ist - vorteilhaft, mit einer Nachspüllösung zu behandeln. Hierzu kann eine gegebenenfalls zusätzlich Chrom-III-Ionen enthaltende Chromsäurelösung verwendet werden. Eine andere Gruppe geeigneter Nachspüllösungen enthält Poly-4-vinylphenol oder das Reaktionsprodukt von Poly-4-vinylphenol mit einem Aldehyd oder einem Keton (US-PSs 3 975 214, 4376000, 4457790, 4 039 353, 4433015).After the phosphate coating has been produced, it is advantageous, particularly if subsequent painting is intended, to be treated with a rinse solution. A chromic acid solution which may additionally contain chromium III ions can be used for this purpose. Another group of suitable rinse solutions contains poly-4-vinylphenol or the reaction product of poly-4-vinylphenol with an aldehyde or a ketone (US Pat. Nos. 3,975,214, 4376000, 4457790, 4,039,353, 4433015).
Obgleich ein Gewichtsverhältnis von Fluorid zu Chlorid von 8: 1 und geringfügig darüber meist von ausreichender Wirkung ist, sieht eine weitere vorteilhafte Ausgestaltung der Erfindung vor, die Metalloberflächen mit einer Phosphatierungslösung in Kontakt zu bringen, in der das Gewichtsverhältnis von Fluorid zu Chlorid auf mindestens 10:1, vorzugsweise mindestens 14:1, eingestellt ist. Diese Arbeitsweise hat insbesondere den Vorzug, daß die Phosphatierungslösung eine gewisse Pufferwirkung gegenüber neuen und gegebenenfalls unerwarteten Chlorideinträgen besitzt.Although a weight ratio of fluoride to chloride of 8: 1 and slightly above is usually sufficient, another advantageous embodiment of the invention provides for the metal surfaces to be brought into contact with a phosphating solution in which the weight ratio of fluoride to chloride is at least 10 : 1, preferably at least 14: 1. This way of working has the particular advantage that the phosphating solution has a certain buffering effect against new and possibly unexpected chloride inputs.
Damit die einzustellende Fluoridkonzentration nicht übermäßig hoch gewählt werden muß, ist es zweckmäßig, darauf zu achten, daß ein unnötig hoher Chlorideintrag entweder beim Ansatz der Phosphatierungslösung selbst oder durch eingeschleppte Lösungsreste aus der Vorbehandlungsstufe vermieden wird. Das heißt, es sollte bereits darauf geachtet werden, daß die Chloridgehalte der Bäder der Vorbehandlungsstufe so niedrig wie möglich gehalten werden. Das gilt für die in zwei Stufen angewandte Reinigungs- und Aktivierungslösung und für eine kombinierte Reinigungs- und Aktivierungslösung. Der Chloridgehalt dieser Lösungen sollte möglichst unter 100 ppm liegen. Beispielsweise werden die in der aktivierenden Vorspülung eingesetzten Aktivierungsmittel in der Regel durch Neutralisation von Titanylsulfat mit Natronlauge und anschließende Behandlung mit Phosphorsäure erhalten. Wegen des beträchtlichen Kochsalzgehaltes der Natronlauge enthalten dann die angesetzten aktivierenden Vorspüllösungen häufig mehr als 400 ppm Chlorid. Bereits in dieser Phase des Verfahrens sollte daher mit Ausgangsstoffen gearbeitet werden, die möglichst wenig Chlorid in das Endprodukt liefern.So that the fluoride concentration to be set does not have to be selected to be excessively high, it is advisable to ensure that an unnecessarily high chloride input is avoided either when preparing the phosphating solution itself or by carrying in solution residues from the pretreatment stage. This means that care should already be taken to ensure that the chloride levels in the baths of the Pretreatment level should be kept as low as possible. This applies to the cleaning and activation solution applied in two stages and to a combined cleaning and activation solution. The chloride content of these solutions should be below 100 ppm if possible. For example, the activating agents used in the activating pre-rinse are generally obtained by neutralizing titanyl sulfate with sodium hydroxide solution and subsequent treatment with phosphoric acid. Because of the considerable sodium chloride content of the sodium hydroxide solution, the activating pre-rinse solutions often contain more than 400 ppm chloride. Already in this phase of the process, you should work with starting materials that deliver as little chloride as possible in the end product.
In gleicher Weise sollte auch bei der Auswahl der Reiniger, die in der Regel mild oder stark alkalisch oder aber sauer sind, auf möglichst weitgehende Chloridfreiheit geachtet werden. Selbstverständlich leistet auch eine besonders gründliche Spülung einen wesentlichen Beitrag, den Eintrag von Chlorid in die Phosphatierungslösung zu unterdrücken.In the same way, when choosing the cleaners, which are generally mild or strongly alkaline or acidic, care should be taken to ensure that they are as free of chloride as possible. Of course, a particularly thorough rinse also makes a significant contribution to suppressing the entry of chloride in the phosphating solution.
Anhand der folgenden Beispiele wird die Erfindung beispielsweise und näher erläutert.The invention is illustrated by way of example and in more detail using the following examples.
Feuerverzinkte Bleche wurden nach folgendem Verfahrensgang behandelt :
- Stufe 1 - Alkalischer Reiniger:
- Stufe 2 - Wasserspülung :
- Stufe 3 - Titan enthaltende Aktivierungslösung :
- Stufe 4 - Zinkphosphatlösung :
- Stufe 5 - Wasserspülung :
- Stufe 6 - Ofentrocknung
- Level 1 - Alkaline cleaner:
- Level 2 - water rinse:
- Level 3 - Titanium Activation Solution:
- Stage 4 - zinc phosphate solution:
- Level 5 - water rinse:
- Level 6 - oven drying
Zur Ermittlung der Wirkung verschiedener Fluoridzusätze (eingebracht über eine Lösung von Natriumhexafluorosilikat) wurden gezielt bestimmte Mengen Natriumchlorid der Phosphatierungslösung zugegeben. Dabei wurde die Chloridkonzentration bis zum Auftreten von Stippen erhöht, wonach Fluorid zugegeben wurde, bis die Stippenbildung unterblieb.To determine the effect of various fluoride additives (introduced via a solution of sodium hexafluorosilicate), specific amounts of sodium chloride were added to the phosphating solution. The chloride concentration was increased until specks appeared, after which fluoride was added until speckling did not occur.
Zur Kontrolle wurde eine frisch angesetzte Phosphatierungslösung stark mit Natriumchlorid verunreinigt, so daß der Gehalt an Chlorid erheblich über dem lag, der zur Stippenbildung erforderlich ist. Danach wurde gestuft Fluorid zugesetzt, bis keine Stippen mehr auftraten.As a control, a freshly prepared phosphating solution was heavily contaminated with sodium chloride, so that the chloride content was considerably higher than that required for speck formation. Fluoride was then added in stages until there were no more specks.
Die Gehalte an Chlorid, Fluorid, das Gewichtsverhältnis Fluorid zu Chlorid und die Beschaffenheit der mit dem Phosphatüberzug versehenen Metalloberfläche sind in der nachfolgenden Tabelle zusammengestellt.
Claims (8)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT86111618T ATE49781T1 (en) | 1985-08-26 | 1986-08-22 | PROCESS FOR APPLYING PHOSPHATE COATINGS. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/769,433 US4595424A (en) | 1985-08-26 | 1985-08-26 | Method of forming phosphate coating on zinc |
| US769433 | 1996-12-19 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0213567A1 EP0213567A1 (en) | 1987-03-11 |
| EP0213567B1 true EP0213567B1 (en) | 1990-01-24 |
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|---|---|---|---|
| EP86111618A Expired - Lifetime EP0213567B1 (en) | 1985-08-26 | 1986-08-22 | Process for applying phosphate coatings |
Country Status (10)
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|---|---|
| US (1) | US4595424A (en) |
| EP (1) | EP0213567B1 (en) |
| JP (1) | JPH06104906B2 (en) |
| AT (1) | ATE49781T1 (en) |
| AU (1) | AU594685B2 (en) |
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| ES (1) | ES2000229A6 (en) |
| GB (1) | GB2179680A (en) |
| MX (1) | MX165325B (en) |
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| JPS5935681A (en) * | 1982-08-24 | 1984-02-27 | Nippon Paint Co Ltd | Method for phosphating metallic surface for coating by cationic electrodeposition |
| JPS621882A (en) * | 1985-06-26 | 1987-01-07 | Nippon Light Metal Co Ltd | Corrosion-resistant hydrophilic film forming material for aluminum materials |
| EP0544650B1 (en) * | 1985-08-27 | 1997-11-26 | HENKEL CORPORATION (a Delaware Corp.) | A process for phosphate-coating metal surfaces |
| DE3537108A1 (en) * | 1985-10-18 | 1987-04-23 | Collardin Gmbh Gerhard | METHOD FOR PHOSPHATING ELECTROLYTICALLY GALVANIZED METALWARE |
| DE3630246A1 (en) * | 1986-09-05 | 1988-03-10 | Metallgesellschaft Ag | METHOD FOR PRODUCING PHOSPHATE COVER AND ITS APPLICATION |
| DE3631759A1 (en) * | 1986-09-18 | 1988-03-31 | Metallgesellschaft Ag | METHOD FOR PRODUCING PHOSPHATE COATINGS ON METAL SURFACES |
| ES2036666T3 (en) * | 1987-08-19 | 1993-06-01 | Metallgesellschaft Ag | PROCEDURE FOR PHOSPHATING METALS. |
| US5073196A (en) * | 1989-05-18 | 1991-12-17 | Henkel Corporation | Non-accelerated iron phosphating |
| US5089349A (en) * | 1989-06-05 | 1992-02-18 | Calgon Corporation | Compositions and method for applying coatings to metallic surfaces |
| US5082511A (en) * | 1989-09-07 | 1992-01-21 | Henkel Corporation | Protective coating processes for zinc coated steel |
| DE3932744A1 (en) * | 1989-09-30 | 1991-04-11 | Herberts Gmbh | Aq. coating soln. for electrophoretic dip lacquer coating - contains at least one zirconium aluminate to improve edge corrosion - and stone impact - resistance |
| US5238505A (en) * | 1991-10-07 | 1993-08-24 | Calgon Corporation | Method for applying tellurium-containing coatings to metallic surfaces using organic acids |
| US5714047A (en) * | 1994-08-05 | 1998-02-03 | Novamax Itb S.R.L. | Acid aqueous phosphatic solution and process using same for phosphating metal surfaces |
| US5597465A (en) * | 1994-08-05 | 1997-01-28 | Novamax Itb S.R.L. | Acid aqueous phosphatic solution and process using same for phosphating metal surfaces |
| US5702759A (en) * | 1994-12-23 | 1997-12-30 | Henkel Corporation | Applicator for flowable materials |
| US5954892A (en) * | 1998-03-02 | 1999-09-21 | Bulk Chemicals, Inc. | Method and composition for producing zinc phosphate coatings on metal surfaces |
| WO1999060186A1 (en) * | 1998-05-20 | 1999-11-25 | Henkel Corporation | Composition and process for treating surfaces of light metals and their alloys |
| US6485580B1 (en) * | 1998-05-20 | 2002-11-26 | Henkel Corporation | Composition and process for treating surfaces or light metals and their alloys |
| JP4736512B2 (en) * | 2005-04-07 | 2011-07-27 | スズキ株式会社 | Outboard motor fuel injection system |
| KR101252448B1 (en) * | 2011-06-28 | 2013-04-16 | 용원기계공업(주) | Crush material interval adjuster of jow crusher |
Family Cites Families (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2312855A (en) * | 1940-09-07 | 1943-03-02 | Parker Rust Proof Co | Method of coating aluminum |
| BE525407A (en) * | 1952-06-18 | |||
| DE1065246B (en) * | 1955-01-26 | 1959-09-10 | Metallgesellschaft Aktiengesellschaft, Frankfurt/M | Process for the production of phosphate coatings on hot-dip galvanized iron surfaces |
| GB812095A (en) * | 1956-02-27 | 1959-04-15 | Pyrene Co Ltd | Improvements relating to the formation of phosphate coatings |
| NL120662C (en) * | 1962-01-26 | |||
| NL293566A (en) * | 1962-06-04 | |||
| GB1040806A (en) * | 1964-04-30 | 1966-09-01 | Pyrene Co Ltd | Improvements in painting metal surfaces |
| DE1621434A1 (en) * | 1967-03-10 | 1971-06-03 | Collardin Gmbh Gerhard | Process for the production of hard, thin zinc phosphate layers |
| GB1178668A (en) * | 1968-03-05 | 1970-01-21 | Lubrizol Corp | Phosphating Solutions containing Lead and Fluoride Ions |
| US3617393A (en) * | 1969-10-08 | 1971-11-02 | Dainippon Toryo Kk | Pretreatment before electrophoretic painting |
| GB1415999A (en) * | 1973-05-29 | 1975-12-03 | Pyrene Chemical Services Ltd | Process for forming phosphate coatings |
| GB1591039A (en) * | 1977-05-03 | 1981-06-10 | Pyrene Chemical Services Ltd | Processes and compositions for coating 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 |
| JPS57152472A (en) * | 1981-03-16 | 1982-09-20 | Nippon Paint Co Ltd | Phosphating method for metallic surface for cation type electrodeposition painting |
| DE3311738A1 (en) * | 1983-03-31 | 1984-10-04 | Metallgesellschaft Ag, 6000 Frankfurt | METHOD FOR PHOSPHATING METAL SURFACES |
| GB8329250D0 (en) * | 1983-11-02 | 1983-12-07 | Pyrene Chemical Services Ltd | Phosphating processes |
| JPS63100185A (en) * | 1986-10-16 | 1988-05-02 | Nippon Parkerizing Co Ltd | Phosphating method |
-
1985
- 1985-08-26 US US06/769,433 patent/US4595424A/en not_active Ceased
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1986
- 1986-06-11 CA CA000511358A patent/CA1293165C/en not_active Expired - Lifetime
- 1986-06-13 AU AU58718/86A patent/AU594685B2/en not_active Expired
- 1986-08-18 MX MX003465A patent/MX165325B/en unknown
- 1986-08-21 DE DE19863628303 patent/DE3628303A1/en not_active Withdrawn
- 1986-08-22 EP EP86111618A patent/EP0213567B1/en not_active Expired - Lifetime
- 1986-08-22 DE DE8686111618T patent/DE3668475D1/en not_active Expired - Fee Related
- 1986-08-22 AT AT86111618T patent/ATE49781T1/en active
- 1986-08-25 ES ES8601334A patent/ES2000229A6/en not_active Expired
- 1986-08-26 GB GB08620633A patent/GB2179680A/en not_active Withdrawn
- 1986-08-26 JP JP61199891A patent/JPH06104906B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06104906B2 (en) | 1994-12-21 |
| GB8620633D0 (en) | 1986-10-01 |
| DE3628303A1 (en) | 1987-03-12 |
| AU5871886A (en) | 1987-03-05 |
| DE3668475D1 (en) | 1990-03-01 |
| ATE49781T1 (en) | 1990-02-15 |
| EP0213567A1 (en) | 1987-03-11 |
| JPS6247489A (en) | 1987-03-02 |
| CA1293165C (en) | 1991-12-17 |
| MX165325B (en) | 1992-11-05 |
| US4595424A (en) | 1986-06-17 |
| ES2000229A6 (en) | 1988-01-16 |
| AU594685B2 (en) | 1990-03-15 |
| GB2179680A (en) | 1987-03-11 |
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