DD299968A5 - Method of applying phosphate coatings - Google Patents
Method of applying phosphate coatings Download PDFInfo
- Publication number
- DD299968A5 DD299968A5 DD339887A DD33988790A DD299968A5 DD 299968 A5 DD299968 A5 DD 299968A5 DD 339887 A DD339887 A DD 339887A DD 33988790 A DD33988790 A DD 33988790A DD 299968 A5 DD299968 A5 DD 299968A5
- Authority
- DD
- German Democratic Republic
- Prior art keywords
- phosphating
- zinc
- iron
- ions
- phosphate coatings
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 15
- 238000000576 coating method Methods 0.000 title claims abstract description 14
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 10
- 239000010452 phosphate Substances 0.000 title claims abstract description 9
- 239000011701 zinc Substances 0.000 claims abstract description 23
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 16
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000956 alloy Substances 0.000 claims abstract description 6
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 abstract description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052742 iron Inorganic materials 0.000 abstract description 5
- -1 iron ion ion Chemical class 0.000 abstract description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001447 ferric ion Inorganic materials 0.000 abstract description 2
- 229910000165 zinc phosphate Inorganic materials 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 235000021317 phosphate Nutrition 0.000 description 7
- 229910001335 Galvanized steel Inorganic materials 0.000 description 5
- 239000008397 galvanized steel Substances 0.000 description 5
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-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 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002828 nitro derivatives Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 1
- HWTDMFJYBAURQR-UHFFFAOYSA-N 80-82-0 Chemical compound OS(=O)(=O)C1=CC=CC=C1[N+]([O-])=O HWTDMFJYBAURQR-UHFFFAOYSA-N 0.000 description 1
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C23C22/364—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 manganese cations
- C23C22/365—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 manganese cations containing also zinc and nickel 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
- C23C22/07—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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/18—Orthophosphates containing manganese cations
- C23C22/182—Orthophosphates containing manganese cations containing also zinc cations
- C23C22/184—Orthophosphates containing manganese cations containing also zinc cations containing also nickel cations
Landscapes
- 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)
Abstract
Bei einem Verfahren zum Aufbringen von Phosphatueberzuegen auf Oberflaechen aus Aluminium und/oder Zink bzw. dessen oder deren Legierungen mit Hilfe von gemaesz der Niedrigzink-Technologie arbeitenden Phosphatierungsloesungen bringt man zwecks Konstanthaltung der Punktzahl an Freier Saeure die Oberflaeche mit einer Phosphatierungsloesung in Kontakt, die eine Mindestkonzentration an Eisen-III-ionen von 1 mg/l enthaelt und der pro m2 behandelter Oberflaeche 50 bis 2 000 mg, vorzugsweise bis 1 000 mg, Eisen-III-ionen zugesetzt werden. Zweckmaeszigerweise enthaelt die PhosphatierungsloesungIn a process for applying phosphate coatings to surfaces of aluminum and / or zinc or its alloys by means of low-zinc phosphate phosphating solutions, the surface is contacted with a phosphating solution to maintain the free acid score 1 mg / l minimum iron ion ion concentration and from 50 to 2,000 mg, preferably up to 1,000 mg, of ferric ion per m2 of surface treated. Zweckmaeszigerweise contains the Phosphatierungsloesung
Description
0,4 bis 1,5g/l Zink0.4 to 1.5 g / l zinc
10 bis 26g/l P2O5 sowie10 to 26 g / l P 2 O 5 as well
0bis1,3g/INi0bis1,3g / IN i
0bis1,3g/IMn0bis1,3g / IM n
0bis1,3g/IMg0bis1,3g / IIIg
enthält.contains.
4. Verfahren nach Anspruch 1,2 oder 3, dadurch gekennzeichnet, daß man die Oberfläche mit einer Phosphatierungslösung in Kontakt bringt, in der das Gewichtsverhältnis von Zn zu P2O5 auf einen Wert im Bereich von (0,075 bis 0,015) :1 und-sofern vorhanden-das Gewichtsverhältnis von Ni, Mn und oder Mg zu Zn auf einen Wert bis 1,5:1 eingestellt ist.A process according to claim 1, 2 or 3, characterized in that the surface is contacted with a phosphating solution in which the weight ratio of Zn to P 2 O 5 is in the range of (0.075 to 0.015): 1 and if present, the weight ratio of Ni, Mn and or Mg to Zn is set to a value of up to 1.5: 1.
5. Verfahren nach einem oder mehreren der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß man die Oberfläche mit einer Phosphatierungslösung in Kontakt bringt, die zusätzlich5. The method according to one or more of claims 1 to 4, characterized in that one brings the surface with a phosphating in contact, in addition
2 bis 25 g/l NO3 2 to 25 g / l NO 3
1 bis 6 g/l CIO3 1 to 6 g / l CIO 3
0,1 bis 2 g/l organische Nitroverbindung0.1 to 2 g / l of organic nitro compound
0,05 bis 0,5g/l NO2 0.05 to 0.5 g / l NO 2
0,02 bis 0,1 g/l Peroxid (ber. als H2O2)0.02 to 0.1 g / l of peroxide (calculated as H 2 O 2 )
oder Mischungen hiervon enthält.or mixtures thereof.
6. Verfahren nach einem oder mehreren der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß man die Oberfläche mit der Phosphatierungslösung bei einer Temperatur im Bereich von 30 bis 700C in Kontakt bringt.6. The method according to one or more of claims 1 to 5, characterized in that one brings the surface with the phosphating at a temperature in the range of 30 to 70 0 C in contact.
Die Erfindung betrifft ein Verfahren zum Aufbringen von Phosphatüberzügen auf Oberflächen aus Aluminium und/oder Zink bzw. dessen oder deren Legierungen mit Hilfe von gemäß der Niedrigzink-Technologie arbeitenden Phosphatierungslösungen. Phosphatierunytlösungen, die gemäß der Niedrigzink-Technologie arbeiten, sind begrifflich solche, die als schichtbildendes Kation überwiegend Zink in einer Konzentration von ca. 0,4 bis 1,5g/l enthalten und in denen das Zn/POvVerhältnis kleiner als ca. 0,C8 ist.The invention relates to a method for applying phosphate coatings on surfaces of aluminum and / or zinc or its or their alloys by means of operating according to the low-zinc phosphatizing solutions. Phosphating solutions which operate according to the low-zinc technology are conceptually those which contain predominantly zinc in a concentration of about 0.4 to 1.5 g / l as the layer-forming cation and in which the Zn / POv ratio is less than about 0.85 is.
Es ist bekannt, dünne Phosphatüberzüge auf Metalloberflächen von Stahl, verzinktem Stahl sowie Aluminium aufzubringen, die für eine nachfolgende elektrophoretische Tauchlackierung eine geeignete Lackgrundlage bilden. Die hierfür eingesetzten Phosphatierungslösungen enthalten üblicherweise Zink-, Nickel-, Mangan-, Magnesium-, Kadmium-, Kupfer-, Kobalt-, Alkali- und/oder Ammoniumionen, Phosphationen, beschleunigend wirkende Zusätze wie Nitrit, Chlorat, Bromat, Peroxid, m-Nitrobenzolsülfonat, Nitrophenol oder Kombinationen hiervon. Für die Behandlung von Aluminium, dessen Legierungen und galvanisch verzinktem Stahl enthalten sie vorzugsweise zusätzlich einfache und/oder komplexe Fluoride. Zusätzliche Anionen, wie Chlorid, Nitrat und Sulfat, dienen der Wahrung der Elektroneutralität. Gegebenenfalls können die Phosphatierungslösungen noch schichtverfeinernde Zusätze, wie Hydroxicarbonsäuren, Aminocarbonsäuren oder kondensierte Phosphate, enthalten. Die Metalloberflächen bestehen dabei zu einem erheblichen Anteil aus Stahl neben wechselnden Mengen verzinktem Stahl sowie einem geringen Anteil an Aluminiumwerkstoffen und werden im Spritz- und/oder Tauchverfahren behandelt. Werden ausschließlich Zinkoberflächen und/oder Aluminiumoberflächen mit der Phosphatierungslösung in Berührung gebracht, stellt man fest, daß die Freie Säure bzw. das Verhältnis Freie Säure zu Gesamtsäure der arbeitenden Phosphatierungslösung ansteigt und die Phosphatierungslösung außerhalb des Gleichgewichtes gerät. Die Folge ist, daß mit zunehmendem Durchsatz die Überzugsausbildung verschlechtert wird und schließlich ganz unterbleibt. Ein Abstumpfen der überschüssigen Säure mit Natriumhydroxid, Ammoniumhydroxid oder anderen Alkalien ist nicht durchführbar, da dann ein Teil der Uadkomponente Zink mitausgefällt wird.It is known to apply thin phosphate coatings on metal surfaces of steel, galvanized steel and aluminum, which form a suitable coating base for a subsequent electrophoretic dip coating. The phosphating solutions used for this purpose usually contain zinc, nickel, manganese, magnesium, cadmium, copper, cobalt, alkali and / or ammonium ions, phosphate ions, accelerating additives such as nitrite, chlorate, bromate, peroxide, Nitrobenzene sulphonate, nitrophenol or combinations thereof. For the treatment of aluminum, its alloys and galvanized steel, they preferably additionally contain simple and / or complex fluorides. Additional anions, such as chloride, nitrate and sulfate, serve to maintain electroneutrality. Optionally, the phosphating solutions may further contain layer-refining additives, such as hydroxycarboxylic acids, aminocarboxylic acids or condensed phosphates. The metal surfaces consist to a considerable extent of steel in addition to changing amounts of galvanized steel and a small proportion of aluminum materials and are treated by spraying and / or dipping. If only zinc surfaces and / or aluminum surfaces are brought into contact with the phosphating solution, it is found that the free acid or the ratio of free acid to total acid of the working phosphating solution increases and the phosphating becomes out of balance. The result is that with increasing throughput, the coating formation is degraded and eventually stops altogether. Dulling the excess acid with sodium hydroxide, ammonium hydroxide or other alkalis is not feasible because then a portion of the Uadkomponente zinc is precipitated mit.
Aufgabe der Erfindung ist es, ein Verfahren zum Aufbringen von Phosphatüberzügen auf Oberflächen aus Zink und/oder Aluminium bzw. dessen oder deren Legierungen mit gemäß der Niedrigzink-Technologie arbeitenden Phosphatierungslösungen bereitzustellen, bei dem ein Anstieg der Freien Säure bzw. des Säureverhältnisses verhindert wird und mithin die Nachteile der bekannton Verfahren vermieden werden, das aber dennoch einfach in der Handhabung sowie wirtschaftlich ist.The object of the invention is to provide a method for applying phosphate coatings on surfaces of zinc and / or aluminum or its alloys or with low-zinc phosphating working, in which an increase in the free acid or the acid ratio is prevented and Consequently, the disadvantages of bekannton method can be avoided, which is still easy to use and economical.
Die Aufgabe wird gelöst, indem das Verfahren der eingangs genannten Art entsprechend der Erfindung derart ausgestaltet wird, daß man die Oberfläche mit einer Phosphat.erungslösung in Kontakt bringt, die eine Mindestkonzentration an Eisen-lll-ionen von 1 mg/l enthält und der pro m2 behandelter Oberfläche 50 bis 2 000 mg Eisen-lll-ionen zugesetzt werden.The object is achieved by the method of the aforementioned type according to the invention is designed such that the surface is brought into contact with a Phosphat.erungslösung containing a minimum concentration of iron-lll-ions of 1 mg / l and the pro m 2 of treated surface 50 to 2,000 mg of iron-l-ions are added.
Die Eisenionen können in Form von Fe-Ill-Ionen, aber auch in Form von Fe-Il-Ionen zusammen mit einem Fe-Il zu Fe-IIi oxidierenden Oxidationsmittel, wie Chlorat, Nitrit, Peroxid, in die Phosphatierungslösung eingebracht werden. Geeignete Verbindungen sind z. B. die Nitrate, Chloride und Fluoride von zwei oder dreiwertigem Eisen sowie Eisen-Ill-Komplexverbindungen von Hydroxicarbonsäuron, Aminocarbonsäuren und dergleichen.The iron ions can be introduced into the phosphating solution in the form of Fe-Ill ions, but also in the form of Fe-II ions together with a Fe-II to Fe-IIi oxidizing oxidant, such as chlorate, nitrite, peroxide. Suitable compounds are for. For example, the nitrates, chlorides and fluorides of di- or trivalent iron and iron-III complex compounds of Hydroxicarbonsäuron, aminocarboxylic acids and the like.
Es ist besonders zweckmäßig, die Eisenionen in Wasser vorgelöster Form in die Phosphatierungslcsung einzubringen.It is particularly useful to introduce the iron ions in water of predissolved form in the Phosphatierungslcsung.
Eine bevorzugte Ausgestaltung der Erfindung besteht darin, die Oberfläche mit einr - Phosphatierungslösung in Kontakt zu bringen, der pro ma behandelter Oberfläche 50 bis 1000mg Eisen-lll-ionan zugesetzt werden. Auch hierbei kann die Dosierung wie oben erwähnt erfolgen.A preferred embodiment of the invention is to bring the surface into contact with a phosphating solution to which 50 to 1000 mg of iron-III-ion are added per ml of treated surface. Again, the dosage can be done as mentioned above.
Das or'indungsgemäße Verfahren ist für alle bekannten gemäß der Niedrigzink-Technologie arbeitenden Phosphatierungslösungen anwendbar.The process according to the invention is applicable to all known phosphating solutions operating according to the low-zinc technology.
Gemäß einer weiteren bevorzugten Ausgestaltung werden solche Lösungen eingesetzt, dieAccording to a further preferred embodiment, such solutions are used, the
0,4 bis 1,5 g/l Zn 10 bis 26g/l P2O6 sowie0.4 to 1.5 g / l Zn 10 to 26 g / l P 2 O 6 as well
Obis 1,3g/l NiObis 1.3g / l Ni
0bis1,3g/IMn0bis1,3g / IM n
0bis1,3g/IMg0bis1,3g / IIIg
enthalten. Bei diesen Lösungen sollte das Gewichtsverhältnis von Zn zu P2O6 auf einen Wert im Bereich von (0,075 bis 0,015):1 und - sofern vorhanden - das Gewichtsverhältnis von Ni, Mn und oder Mg zu Zn auf einen Wert bis 1,5:1 eingestellt sein. Gemäß einer weiteren vorteilhaften Ausgestaltung der Erfindung kommen Phosphatierungslösungen zum Einsatz, die als Beschleunigercontain. In these solutions, the weight ratio of Zn to P 2 O 6 should be in the range of (0.075 to 0.015): 1 and, if present, the weight ratio of Ni, Mn and or Mg to Zn to a value of 1.5: 1 be set. According to a further advantageous embodiment of the invention, phosphating solutions are used which act as accelerators
2 bis 25 g/l NO3 2 to 25 g / l NO 3
1 bis 6 g/l CIO3 1 to 6 g / l CIO 3
0,1 bis 2 g/l organische Nitroverbindung0.1 to 2 g / l of organic nitro compound
C,05bis0,5g/INO2 C, 05 to 0.5g / INO 2
0,02 bis 0,1 g/l Peroxid (ber. als H2O2)0.02 to 0.1 g / l of peroxide (calculated as H 2 O 2 )
oder Mischungen hiervon enthalten.or mixtures thereof.
Die Phosphatierungslösungen können auf herkömmliche Weise appliziert werden. Besonders geeignete Applikationsformen sind Spritzen und/oder Tauchen, wobei eine Temperatur im Bereich von 30 bis 7O0C bevorzugt ist.The phosphating solutions can be applied in a conventional manner. Particularly suitable of application include spray and / or dipping, wherein a temperature in the range of 30 to 7O 0 C is preferred.
Während Arbeitspausen ist durch Zugabe von Eisen-lll-ionen dafür Sorge zu tragen, daß die Mindestkonzentration von 1 mg/1 aufrechterhalten wird.During breaks, the addition of ferric ions should ensure that the minimum concentration of 1 mg / l is maintained.
Das erfindungsgemäße Verfahren eignet sich insbesondere zur Behandlung von Reinaluminium und Legierungen, z.B. der Qualitäten AIMgSi, AIMg und AIMgMn.The process according to the invention is particularly suitable for the treatment of pure aluminum and alloys, e.g. of the qualities AIMgSi, AIMg and AIMgMn.
Hinsichtlich der Überzugsbildung auf Zinkoberflächen können Werkstücke aus massivem Zink, insbesondere aber aus schmelztauch· odar elektrolytisch verzinktem Stahl, behandelt werden. Geeignete Werkstoffe sind weiterhin massive oder auf Stahl aufgebrachte Zinklegierungen mit z. B. Ni, Fe oder Al.With regard to the formation of coatings on zinc surfaces, workpieces made of solid zinc, but in particular of hot-dip or electrolytically galvanized steel, can be treated. Suitable materials are still massive or steel-applied zinc alloys with z. For example, Ni, Fe or Al.
Mit Hilfe des erfindungsgemäßen Verfahrens gelingt es, selbst über einen längeren Zeitpunkt hinweg Phosphatüberzüge zuWith the aid of the method according to the invention it is possible to obtain phosphate coatings even over a relatively long time
erzeugen, die durchweg gleichmäßig und geschlossen sind. Diese Überzüge eignen sich in besonderer Weise für eine nachfolgende elektrophoretisch^ Tauchlackierung.produce consistently uniform and closed. These coatings are particularly suitable for subsequent electrophoretic dipcoating.
Die Erfindung wird anhand der nachfolgenden Beispiele beispielsweise und näher erläutert.The invention will be explained by way of example with reference to the following examples.
In einem 10-l-Phosphatierungsbehälter wurden alternierend zuvor entfettete und gebeizte Bleche aus Aluminium (70%) der Qualität AIMgSi und AIMg3 und elektrolytisch verzinktem Stahl (30%) mit einer Phosphatierungslösung behandelt, dieIn a 10 l phosphating container, previously degreased and pickled aluminum (70%) sheets of AIMgSi and AIMg3 grade and electrolytically galvanized steel (30%) were alternately treated with a phosphating solution containing
0,7 g/l Zn 0,7 g/l Ni 1.0g/IMn 3,4g/l Na 11.5g/IP2OB 3,0g/l NO3 0,5 g/l F 0,1 g/l NO2 0.7g / l Zn 0.7g / l Ni 1.0g / IMn 3.4g / l Na 11.5g / IP 2 O B 3.0g / l NO 3 0.5g / l F 0.1g / l NO 2
enthielt. Die Temperatur der Lösung betrug 55 bis 60°C. Die Behandlung erfolgte im Spritzen für die Dauer von 3min. Die Freie Säure der Phosphatierungslösung lag bei 1,0.contained. The temperature of the solution was 55 to 60 ° C. The treatment was done by spraying for 3min. The free acid of the phosphating solution was 1.0.
Durch Zugabe von Eisen-Ill-Zitrat war die Eisen-Ill-Konzentration bei Inbetriebnahme der Phosphatierungslösung auf 2 mg/l eingestellt worden.By adding iron-III citrate, the iron-III concentration had been adjusted to 2 mg / L upon start-up of the phosphating solution.
Im Verlauf des Durchsatzes wurden der Phosphatierungslösung von 101250 mg/m2 Oberfläche Eisen-Ill-Zitrat (bar. als Te) zugegeben. Wie die nachfolgende Tabelle zeigt, war die Zahl der Freie-Säure-Punkte praktisch konstant Der erhaltene Phosphatüberzug war durchweg gleichmäßig und geschlossen.In the course of the throughput, the phosphating solution of 101250 mg / m 2 surface iron-III citrate (bar as Te) was added. As shown in the table below, the number of free acid points was virtually constant. The resulting phosphate coating was consistently uniform and closed.
Durchsatz (m2) OA Oft U 1^6 2J 2,8 3,2 Throughput (m 2 ) OA Often U 1 ^ 6 2J 2,8 3,2
Freie-Säure-Punkte 1,0 1,1 1,1 1,0 1,0 1,1 1,0Free Acid Points 1.0 1.1 1.1 1.0 1.0 1.1 1.0
VergleichsbeispielComparative example
Als Vergleichsbeispiel wurden Bleche gleicher Qualität und in gleicher Weise durch die vorgenannte Phosphatierungslösung, die jedoch keine Eisen-lll-ionen enthielt und nicht mit Eisen-lll-ionen ergänzt worden war, durchgesetzt. Entsprechend zunehmendem Durchsatz veränderte sich die Zahl der Freie-Säure-Punkte wie unten angegeben. Während anfänglich hochwertige Phosphatüberzüge erhalten wurden, war mit steigender Punktzahl eine Verschlechterung der Qualität festzustellen. Ab einer Zahl Freie-Säure-Punkte von 1,50 war überhaupt keine Überzugsausbildung zu beobachten.As a comparative example sheets of the same quality and in the same way by the aforementioned phosphating, but no iron-lll-ions contained and was not supplemented with iron-lll-ion enforced. As the throughput increased, the number of free-acid points changed as indicated below. While high-quality phosphate coatings were initially obtained, quality deteriorated as the score increased. From a number of free-acid points of 1.50, no coating formation was observed at all.
Durchsatz (m2) 0,4 0,8 1,2 1,6 2,0 2,4 2,8 3,2Throughput (m 2 ) 0.4 0.8 1.2 1.6 2.0 2.4 2.8 3.2
Freie-Säure-Punkte 1,0 1,15 1,25 1,35 1,45 1,50 1,55 1,60Free Acid Points 1.0 1.15 1.25 1.35 1.45 1.50 1.55 1.60
Claims (3)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3839802 | 1988-11-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DD299968A5 true DD299968A5 (en) | 1992-05-14 |
Family
ID=6367867
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DD339887A DD299968A5 (en) | 1988-11-25 | 1990-04-19 | Method of applying phosphate coatings |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0370535B1 (en) |
| JP (1) | JP2845246B2 (en) |
| CA (1) | CA1334371C (en) |
| DD (1) | DD299968A5 (en) |
| DE (1) | DE58902702D1 (en) |
| ES (1) | ES2036023T3 (en) |
| GB (1) | GB2226829B (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5238506A (en) * | 1986-09-26 | 1993-08-24 | Chemfil Corporation | Phosphate coating composition and method of applying a zinc-nickel-manganese phosphate coating |
| DE3828676A1 (en) * | 1988-08-24 | 1990-03-01 | Metallgesellschaft Ag | PHOSPHATING PROCESS |
| DE3918136A1 (en) * | 1989-06-03 | 1990-12-06 | Henkel Kgaa | METHOD FOR PRODUCING MANAGE-CONTAINING PHOSPHATE COATINGS ON METAL SURFACES |
| EP0439377A1 (en) * | 1990-01-26 | 1991-07-31 | Ppg Industries, Inc. | Method of applying a zinc-nickel-manganese phosphate coating. |
| US5261973A (en) * | 1991-07-29 | 1993-11-16 | Henkel Corporation | Zinc phosphate conversion coating and process |
| US5645706A (en) * | 1992-04-30 | 1997-07-08 | Nippondenso Co., Ltd. | Phosphate chemical treatment method |
| JPH05306497A (en) | 1992-04-30 | 1993-11-19 | Nippondenso Co Ltd | Phophatizing chemical conversion treatment |
| DE4228470A1 (en) * | 1992-08-27 | 1994-03-03 | Henkel Kgaa | Process for phosphating steel strips galvanized on one side |
| DE4243214A1 (en) * | 1992-12-19 | 1994-06-23 | Metallgesellschaft Ag | Process for the production of phosphate coatings |
| US5797987A (en) * | 1995-12-14 | 1998-08-25 | Ppg Industries, Inc. | Zinc phosphate conversion coating compositions and process |
| US5900073A (en) * | 1996-12-04 | 1999-05-04 | Henkel Corporation | Sludge reducing zinc phosphating process and composition |
| JP3366826B2 (en) * | 1997-04-30 | 2003-01-14 | 本田技研工業株式会社 | Zinc phosphate treatment agent for aluminum alloy |
| JP4019723B2 (en) * | 2001-02-23 | 2007-12-12 | 株式会社デンソー | Electrolytic phosphate chemical treatment method |
| RU2560891C1 (en) * | 2014-05-05 | 2015-08-20 | Федеральное государственное унитарное предприятие федеральный научно-производственный центр "Производственное объединение "Старт" им. М.В. Проценко" (ФГУП ФНПЦ "ПО "Старт" им. М.В. Проценко") | Method of iron-cobalt alloy phosphating |
| PL3280831T3 (en) * | 2015-04-07 | 2025-03-10 | Chemetall Gmbh | Method for nickel-free phosphating metal surfaces |
| RU2624566C1 (en) * | 2016-02-15 | 2017-07-04 | Федеральное государственное унитарное предприятие федеральный научно-производственный центр "Производственное объединение "Старт" им. М.В. Проценко" (ФГУП ФНПЦ "ПО "Старт" им. М.В. Проценко") | Method of phosphatory of magnetic-aluminium alloys of type permalloy (versions) |
| US11124880B2 (en) | 2016-04-07 | 2021-09-21 | Chemetall Gmbh | Method for nickel-free phosphating metal surfaces |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2738281A1 (en) * | 1977-08-25 | 1979-03-01 | Metallgesellschaft Ag | METHOD FOR PHOSPHATING METALS |
| DE2738283A1 (en) * | 1977-08-25 | 1979-03-01 | Metallgesellschaft Ag | METHOD FOR PHOSPHATING METALS |
| DE2738282A1 (en) * | 1977-08-25 | 1979-03-01 | Metallgesellschaft Ag | METHOD FOR APPLYING PHOSPHATE |
| US4278477A (en) * | 1980-03-19 | 1981-07-14 | Amchem Products, Inc. | Metal treatment |
| US4486241A (en) * | 1981-09-17 | 1984-12-04 | Amchem Products, Inc. | Composition and process for treating steel |
| DE3245411A1 (en) * | 1982-12-08 | 1984-07-05 | Gerhard Collardin GmbH, 5000 Köln | METHOD FOR PHOSPHATING ELECTROLYTICALLY GALVANIZED METAL GOODS |
| FR2569203B1 (en) * | 1984-08-16 | 1989-12-22 | Produits Ind Cie Fse | PROCESS FOR THE TREATMENT BY CHEMICAL CONVERSION OF SUBSTRATES IN ZINC OR IN ONE OF ITS ALLOYS, CONCENTRATE AND BATH USED FOR THE IMPLEMENTATION OF THIS PROCESS |
| JPS63100185A (en) * | 1986-10-16 | 1988-05-02 | Nippon Parkerizing Co Ltd | Phosphating method |
-
1989
- 1989-07-22 ES ES198989201936T patent/ES2036023T3/en not_active Expired - Lifetime
- 1989-07-22 EP EP89201936A patent/EP0370535B1/en not_active Expired - Lifetime
- 1989-07-22 DE DE8989201936T patent/DE58902702D1/en not_active Expired - Lifetime
- 1989-08-02 CA CA000607371A patent/CA1334371C/en not_active Expired - Fee Related
- 1989-08-04 GB GB8917936A patent/GB2226829B/en not_active Expired - Fee Related
- 1989-11-21 JP JP1300984A patent/JP2845246B2/en not_active Expired - Lifetime
-
1990
- 1990-04-19 DD DD339887A patent/DD299968A5/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| EP0370535B1 (en) | 1992-11-11 |
| EP0370535A1 (en) | 1990-05-30 |
| GB2226829B (en) | 1993-01-20 |
| JP2845246B2 (en) | 1999-01-13 |
| GB8917936D0 (en) | 1989-09-20 |
| JPH02190478A (en) | 1990-07-26 |
| ES2036023T3 (en) | 1993-05-01 |
| DE58902702D1 (en) | 1992-12-17 |
| GB2226829A (en) | 1990-07-11 |
| CA1334371C (en) | 1995-02-14 |
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