EP0327153B1 - Process for applying phosphate coatings to metals - Google Patents
Process for applying phosphate coatings to metals Download PDFInfo
- Publication number
- EP0327153B1 EP0327153B1 EP89200142A EP89200142A EP0327153B1 EP 0327153 B1 EP0327153 B1 EP 0327153B1 EP 89200142 A EP89200142 A EP 89200142A EP 89200142 A EP89200142 A EP 89200142A EP 0327153 B1 EP0327153 B1 EP 0327153B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- individual parts
- solution
- process according
- ions
- 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 description 30
- 229910019142 PO4 Inorganic materials 0.000 title claims description 29
- 238000000034 method Methods 0.000 title claims description 28
- 239000010452 phosphate Substances 0.000 title claims description 27
- 238000000576 coating method Methods 0.000 title claims description 18
- 229910052751 metal Inorganic materials 0.000 title claims description 5
- 239000002184 metal Substances 0.000 title claims description 5
- 150000002739 metals Chemical class 0.000 title 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 32
- 235000021317 phosphate Nutrition 0.000 claims description 28
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 17
- 229910052742 iron Inorganic materials 0.000 claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 229910002651 NO3 Inorganic materials 0.000 claims description 12
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000011701 zinc Substances 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 229910000831 Steel Inorganic materials 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 239000010959 steel Substances 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- -1 nitrate ions Chemical class 0.000 claims description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- 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 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- FEWJPZIEWOKRBE-LWMBPPNESA-N levotartaric acid Chemical compound OC(=O)[C@@H](O)[C@H](O)C(O)=O FEWJPZIEWOKRBE-LWMBPPNESA-N 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims 2
- 239000011651 chromium Substances 0.000 claims 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N iron (II) ion Substances [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims 1
- 229910001431 copper ion Inorganic materials 0.000 claims 1
- 229910001453 nickel ion Inorganic materials 0.000 claims 1
- 239000000243 solution Substances 0.000 description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 7
- 230000009189 diving Effects 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 235000011007 phosphoric acid Nutrition 0.000 description 6
- 238000005554 pickling Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 5
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 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 3
- 229910000165 zinc phosphate Inorganic materials 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000013505 freshwater Substances 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 1
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 1
- ONMOULMPIIOVTQ-UHFFFAOYSA-M 3-Nitrobenzene sulphonate Chemical compound [O-][N+](=O)C1=CC=CC(S([O-])(=O)=O)=C1 ONMOULMPIIOVTQ-UHFFFAOYSA-M 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 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
- 150000001768 cations Chemical class 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229940050410 gluconate Drugs 0.000 description 1
- 229940005740 hexametaphosphate Drugs 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- JCYPECIVGRXBMO-FOCLMDBBSA-N methyl yellow Chemical compound C1=CC(N(C)C)=CC=C1\N=N\C1=CC=CC=C1 JCYPECIVGRXBMO-FOCLMDBBSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012487 rinsing solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000176 sodium gluconate Substances 0.000 description 1
- 235000012207 sodium gluconate Nutrition 0.000 description 1
- 229940005574 sodium gluconate Drugs 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—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
- C23C22/78—Pretreatment of the material to be coated
Description
Die Erfindung betrifft ein verfahren zur Erzeugung von Phosphatüberzügen auf mindestens teilweise Eisen- oder Stahloberflächen aufweisenden Einzelteilen aus Metall mittels wäßriger Phosphatierungslösungen, die Zink-, Phosphat-, Nitrat-, Fluorid-, Nickel-, Kupfer- und autokatalytisch gebildete Nitritionen enthalten sowie praktisch frei von Eisen II-Ionen sind.The invention relates to a process for the production of phosphate coatings on at least partially iron or steel surfaces having individual parts made of metal by means of aqueous phosphating solutions containing zinc, phosphate, nitrate, fluoride, nickel, copper and autocatalytically formed nitrite ions and practically free of iron are II ions.
Es ist bekannt, mindestens teilweise Stahl- oder Eisenoberflächen aufweisende Werkstücke, beispielsweise Einzelteile, wie Luftfiltergehäuse, tiefgezogene Bremsenteile, Fahrzeugräder sowie weitere Automobilzubehörteile, mit Zinkphosphatüberzügen zu versehen. Hierzu dienen u.a. Phosphatierungslösungen, die neben Zink- und Phosphationen Nitrationen als Beschleuniger enthalten. Derartige Phosphatierungslösungen arbeiten üblicherweise "auf der Eisenseite", d.h. während des Einsatzes reichert sich durch den Beizangriff von der Eisen- oder Stahloberfläche gelöstes Eisen in der Lösung an. Um den Gehalt an Eisen II-Ionen unterhalb der Grenze zu halten, bei der eine Beeinträchtigung der Qualität des Phosphatüberzuges aufzutreten beginnt, ist es bekannt, beispielsweise gezielt Chlorat zuzudosieren, so daß die Eisen II-Konzentration im Bereich von 0,05 bis 1 Gew.% gehalten wird (EP-B-0 045 110).It is known to provide at least partially steel or iron workpieces, for example individual parts such as air filter housings, deep-drawn brake parts, vehicle wheels and other automotive accessories, with zinc phosphate coatings. Among other things, Phosphating solutions that contain nitrate ions as accelerators in addition to zinc and phosphate ions. Such phosphating solutions usually work "on the iron side", i.e. during use, iron pickling from the iron or steel surface accumulates in the solution due to the pickling attack. In order to keep the content of iron II ions below the limit at which an impairment of the quality of the phosphate coating begins to occur, it is known to meter chlorate in a targeted manner, for example, so that the iron II concentration in the range from 0.05 to 1% by weight % is kept (EP-B-0 045 110).
Eine andere Art von Zinkphosphatverfahren, die in der Regel mit hohen Nitratgehalten und bei höheren Temperaturen arbeiten, zeichnet sich dadurch aus, daß die im Einsatz befindlichen Phosphatierungslösungen praktisch frei von Eisen II-Ionen sind. Bei ihnen bildet sich autokatalytisch Nitrit, das die Eisen II-Ionen in Eisen III-Ionen überführt, die ihrerseits mit Phosphationen schwerlösliches Eisenphosphat bilden (DE-A-25 40 684).Another type of zinc phosphate process, which usually works with high nitrate contents and at higher temperatures, is characterized in that the phosphating solutions used are practically free of iron II ions. In them, nitrite, which contains the iron II ions, forms autocatalytically Iron III ions are transferred, which in turn form poorly soluble iron phosphate with phosphate ions (DE-A-25 40 684).
Ein ebenfalls autokatalytisch Nitrit bildendes Tauchverfahren auf Basis Zinkphosphat ist in FR-A-2 235 203 beschrieben. Neben Zink und P₂O₅ in Mengen von 4 bis 20 g/l bzw. 3 bis 20 g/l enthalten die dabei zur Anwendung kommenden Lösungen noch 20 bis 50 g/l Nitrat, 0,001 bis 0,5 g/l Nickel, 0,001 bis 0,050 g/l Kupfer, 0,1 bis 2,0 g/l Fluorid und 0,01 bis 0,5 g/l Nitrit. Das Gewichtsverhältnis von freiem P₂O₅ zu Gesamt-P₂O₅ soll (0,30 bis 0,65) : 1, die Anwendungstemperatur 50 bis 80°C betragen.A dip process based on zinc phosphate, which also forms autocatalytic nitrite, is described in FR-A-2 235 203. In addition to zinc and P₂O₅ in amounts of 4 to 20 g / l or 3 to 20 g / l, the solutions used also contain 20 to 50 g / l nitrate, 0.001 to 0.5 g / l nickel, 0.001 to 0.050 g / l copper, 0.1 to 2.0 g / l fluoride and 0.01 to 0.5 g / l nitrite. The weight ratio of free P₂O₅ to total P₂O₅ should (0.30 to 0.65): 1, the application temperature 50 to 80 ° C.
Den Verfahren gemäß EP-B-45 110 und DE-A-2 540 684 ist gemeinsam, daß die Ausbildung des Phosphatüberzuges mit 5 bis 15 min. eine vergleichsweise lange Behandlungsdauer erfordert. Beim Verfahren gemäß FR-A-2 235 203 ist zwar angegeben, daß z. B. bei Drahtdurchlaufanlagen eine Kontaktzeit zwischen Phosphatierungslösung und Werkstückoberfläche von 10 sec. ausreichend ist. Die Dauer der Tauchbehandlung wird jedoch mit 1 bis 10 min. als Normalfall bezeichnet, so daß letztlich auch hierbei die Behandlungszeit vergleichsweise lang ist.The processes according to EP-B-45 110 and DE-A-2 540 684 have in common that the formation of the phosphate coating takes 5 to 15 minutes. requires a comparatively long treatment period. In the process according to FR-A-2 235 203 it is stated that, for. B. in wire feed systems, a contact time between phosphating solution and workpiece surface of 10 seconds is sufficient. However, the duration of the diving treatment is 1 to 10 minutes. referred to as the normal case, so that the treatment time is ultimately comparatively long.
In der Praxis sind Behandlungszeiten von 5 bis 15 min. oder aber von ca. 1 bis 10 min. jedoch häufig nur mit vergleichsweise großem apparativen Aufwand realisierbar, d. h. es wäre wünschenswert, Verfahren, die in kürzerer Zeit durchführbar sind, zur Verfügung zu haben. Dies ist insbesondere dann wünschenswert, wenn die Oberflächenbehandlung in vorgegebene Fertigungsabläufe, die bei der Behandlung von Einzelteilen, z. B. der vorgenannten Art, von Bedeutung sind, integriert werden soll.In practice, treatment times are 5 to 15 minutes. or from about 1 to 10 min. however, can often only be achieved with a comparatively large expenditure on equipment, d. H. it would be desirable to have procedures that can be performed in a shorter time. This is particularly desirable if the surface treatment in predetermined manufacturing processes that are used in the treatment of individual parts, eg. B. of the aforementioned type, are of importance, should be integrated.
Aufgabe der Erfindung ist es, ein Verfahren zur Erzeugung von Phosphatüberzügen auf mindestens teilweise Eisen- oder Stahloberflächen aufweisenden Einzelteilen bereitzustellen, das den Nachteil der langen Behandlungsdauer nicht aufweist, sondern in kurzer Zeit zu Phosphatüberzügen führt, die dennoch von hoher Qualität sind.The object of the invention is to provide a method for producing phosphate coatings on individual parts having at least partially iron or steel surfaces To provide, which does not have the disadvantage of the long treatment time, but leads to phosphate coatings in a short time, which are nevertheless of high quality.
Die Aufgabe wird gelöst, indem das Verfahren der eingangs genannten Art entsprechend der Erfindung in der weise ausgestaltet wird, daß man die Einzelteile bei einer Temperatur im Bereich von 60 bis 100°C für die Dauer von 3 bis 30 sec. mit einer Phosphatierungslösung in Kontakt bringt, die
10 bis 80 g/l Zink
12 bis 80 g/l Phosphat (ber. als P₂O₅)
40 bis 150 g/l Nitrat sowie zusätzlich
0,1 bis 5 g/l Fluorid
0,01 bis 10 g/l Nickel
0,001 bis 0,1 g/l Kupfer
enthält, in der das Verhältnis von Freier Säure zu Gesamtsäure auf (0,1 bis 0,3):1 eingestellt ist und die mindestens 80 Punkte Gesamtsäure aufweist.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 individual parts are in contact with a phosphating solution at a temperature in the range from 60 to 100 ° C. for a period of 3 to 30 seconds brings that
10 to 80 g / l zinc
12 to 80 g / l phosphate (calculated as P₂O₅)
40 to 150 g / l nitrate as well as additional
0.1 to 5 g / l fluoride
0.01 to 10 g / l nickel
0.001 to 0.1 g / l copper
contains, in which the ratio of free acid to total acid is set to (0.1 to 0.3): 1 and which has at least 80 points total acid.
Obgleich - wie oben dargelegt - Nitrit autokatalytisch gebildet wird, kann es in der Startphase des Verfahrens erforderlich sein, der Phosphatierungslösung Nitrit, beispielsweise in einer Menge von 0,03 bis 0,2 g/l, zuzusetzen.Although - as explained above - nitrite is formed autocatalytically, it may be necessary to add nitrite to the phosphating solution, for example in an amount of 0.03 to 0.2 g / l, in the initial phase of the process.
Das erfindungsgemäße Verfahren dient insbesondere der Behandlung von Einzelteilen, deren Eisen- oder Stahloberfläche Legierungszusätze bis maximal 5 Gew.% aufweist.The method according to the invention is used in particular for the treatment of individual parts whose iron or steel surface has alloy additions of up to a maximum of 5% by weight.
Die einzelnen Komponenten der Phosphatierungslösung, wie Zink, Phosphat, Nitrat usw., werden meist, wie in der Phosphatiertechnik üblich, gemeinsam als saures Phosphatierkonzentrat vorgelöst und in dieser Form in die Phosphatierungslösung eingebracht. Die Bemessung der einzelnen Bestandteile erfolgt in der Weise, daß die geforderten Konzentrationsbereiche in der Phosphatierungslösung resultieren. Um das notwendige Verhältnis von Freier Säure zu Gesamtsäure einzustellen, müssen ggf. weitere Kationen aus der Alkali- und/oder Ammoniumgruppe mitverwendet werden. Ggf. kann auch Zinkoxid und/oder Zinkcarbonat, die der Phosphatierungslösung in Pulverform oder als wäßrige Aufschlämmung zugegeben werden, verwendet werden. Zur Ermittlung der Freien Säure bzw. Gesamtsäure werden jeweils 10 ml Badprobe mit n/10 NaOH gegen den ersten bzw. zweiten Umschlag der Phosphorsäure titriert, wobei als Indikator z.B. der Farbumschlag von Dimethylgelb (Freie Säure) bzw. Phenolphthalein (Gesamtsäure) dient. Die verbrauchten ml an n/10 NaOH entsprechen der Freien Säure bzw. der Gesamtsäure in Punkten.The individual components of the phosphating solution, such as zinc, phosphate, nitrate, etc., are usually, as is customary in phosphating technology, pre-dissolved together as an acidic phosphating concentrate and introduced into the phosphating solution in this form. The individual components are dimensioned in such a way that the required concentration ranges result in the phosphating solution. To set the necessary ratio of free acid to total acid, additional cations from the alkali and / or ammonium group may have to be used. Possibly. can also zinc oxide and / or zinc carbonate, which the Phosphating solution in powder form or as an aqueous slurry can be used. To determine the free acid or total acid, titrate 10 ml bath sample with n / 10 NaOH against the first or second change in phosphoric acid, using the color change of dimethyl yellow (free acid) or phenolphthalein (total acid), for example, as an indicator. The ml of n / 10 NaOH consumed correspond to the free acid or the total acid in points.
Der Gehalt an Nitritpunkten wird in der Regel nach der Saccharometermethode bestimmt. Hierzu werden 50 ml Badlösung mit 2 bis 5 g Sulfaminsäure versetzt. Die dabei gebildete Gasmenge in ml ist gleich der Punktzahl. Ein Gas-Punkt entspricht einem Gehalt von 46 mg/l NO₂ in der Phosphatierungslösung.The content of nitrite points is usually determined using the saccharometer method. For this, 50 ml of bath solution are mixed with 2 to 5 g of sulfamic acid. The amount of gas generated in ml is equal to the number of points. A gas point corresponds to a content of 46 mg / l NO₂ in the phosphating solution.
Der Kontakt der Einzelteile mit der Phosphatierungslösung erfolgt vorzugsweise im Tauchen oder Fluten.The contact of the individual parts with the phosphating solution is preferably carried out by dipping or flooding.
Die mit dem erfindungsgemäßen Verfahren erzeugten Phosphatüberzüge besitzen - je nach Badzusammensetzung, Behandlungszeit und Behandlungstemperatur - ein Schichtgewicht von 2,0 bis 10 g/m².Depending on the bath composition, treatment time and treatment temperature, the phosphate coatings produced by the process according to the invention have a layer weight of 2.0 to 10 g / m².
Eine bevorzugte Ausgestaltung der Erfindung besteht darin, die Einzelteile mit einer Phosphatierungslösung in Kontakt zu bringen, die
30 bis 60 g/l Zink
30 bis 50 g/l Phosphat (ber. als P₂O₅)
65 bis 100 g/l Nitrat
0,5 bis 3,0 g/l Fluorid
0,02 bis 0,5 g/l Nickel und
0,001 bis 0,1 g/l Kupfer
enthält.A preferred embodiment of the invention consists in bringing the individual parts into contact with a phosphating solution
30 to 60 g / l zinc
30 to 50 g / l phosphate (calculated as P₂O₅)
65 to 100 g / l nitrate
0.5 to 3.0 g / l fluoride
0.02 to 0.5 g / l nickel and
0.001 to 0.1 g / l copper
contains.
Die Bildungsgeschwindigkeit des Phosphatüberzuges kann erhöht werden, wenn entsprechend einer weiteren vorteilhaften Ausbildung der Erfindung die Einzelteile mit einer Phosphatierungslösung in Kontakt gebracht werden, die weitere beschleunigend wirkende Zusätze enthalten. Derartige beschleunigend wirkende Zusätze können beispielsweise Chlorat, Bromat, Peroxid, m-Nitrobenzolsulfonat, Nitrophenol oder Kombinationen hiervon sein.The rate of formation of the phosphate coating can be increased if, in accordance with a further advantageous embodiment of the invention, the individual parts are brought into contact with a phosphating solution which contains further accelerating additives. Such accelerating additives can be, for example, chlorate, bromate, peroxide, m-nitrobenzenesulfonate, nitrophenol or combinations thereof.
Eine weitere Verbesserung der Eigenschaften des Phosphatüberzuges ist erzielbar, wenn entsprechend einer weiteren vorteilhaften Ausgestaltung der Erfindung die Einzelteile mit einer Phosphatierungslösung in Kontakt gebracht werden, die zusätzliche 0,1 bis 10 g/l, vorzugsweise 1 bis 5 g/l, Mangan enthält.A further improvement in the properties of the phosphate coating can be achieved if, according to a further advantageous embodiment of the invention, the individual parts are brought into contact with a phosphating solution which contains an additional 0.1 to 10 g / l, preferably 1 to 5 g / l, of manganese.
Zur Erreichung niedriger Überzugsgewichte ist es entsprechend einer weiteren zweckmäßigen Ausführungsform der Erfindung vorteilhaft, die Einzelteile mit einer Phosphatierungslösung in Kontakt zu bringen, die zusätzlich 0,05 bis 3 g/l Weinsäure und/oder Zitronensäure enthält. Eine weitere vorteilhafte Ausgestaltung der Erfindung besteht darin, die Einzelteile vor der Phosphatierung zu reinigen, ggf. von Rost, Zunder und Phosphatschicht zu befreien und zu aktivieren sowie nach der Phosphatierung mit einer Nachspüllösung zu passivieren, wobei jeder der Verfahrensschritte während einer Dauer von 3 bis 30 sec durchgeführt wird.To achieve low coating weights, it is advantageous according to a further advantageous embodiment of the invention to bring the individual parts into contact with a phosphating solution which additionally contains 0.05 to 3 g / l tartaric acid and / or citric acid. Another advantageous embodiment of the invention is to clean the individual parts before phosphating, if necessary to free them of rust, scale and phosphate layer and to activate them, and to passivate them with a rinse solution after phosphating, each of the process steps lasting from 3 to 30 sec is carried out.
In diesem Zusammenhang hat es sich als vorteilhaft erwiesen, zur Reinigung mit einer alkalischen Reinigerlösung einer Temperatur im Bereich zwischen 60 und 100°C und einer Konzentration im Bereich von 20 bis 200 g/l zu arbeiten. Besonders günstige Reiniger sind solche auf Basis Natriumhydroxid, Glukonat, Phosphat mit einem zusätzlichen Gehalt von Carbonat, Silikat und Borat sowie Tensid. Der Einsatz des Reinigers erfolgt vorzugsweise im Spritzen.In this context, it has proven to be advantageous to work with an alkaline cleaning solution at a temperature in the range between 60 and 100 ° C. and a concentration in the range from 20 to 200 g / l for cleaning. Are particularly cheap cleaners those based on sodium hydroxide, gluconate, phosphate with an additional content of carbonate, silicate and borate and surfactant. The cleaner is preferably used in spraying.
Für die ggf. erforderliche Befreiung der Metalloberfläche von Rost, Zunder und Phosphatschichten haben sich Schwefelsäure- oder Phosphorsäurelösungen einer Temperatur im Bereich von 60 bis 100°C und einer Konzentration im Bereich von 5 bis 50 Gew.% als vorteilhaft erwiesen. Entsprechend einer bevorzugten Weiterbildung der Erfindung wird eine Schwefel- oder Phosphorsäure eingesetzt, die zusätzlich Eisen II- und/oder Eisen III-Ionen in einer Konzentration im Bereich von 1 bis 50 g/l enthält. Bei Anwendung derartiger Beizlösungen ist das erzielte Resultat besonders günstig.Sulfuric acid or phosphoric acid solutions at a temperature in the range from 60 to 100 ° C. and a concentration in the range from 5 to 50% by weight have proven to be advantageous for the removal of rust, scale and phosphate layers that may be required. According to a preferred development of the invention, a sulfuric or phosphoric acid is used which additionally contains iron II and / or iron III ions in a concentration in the range from 1 to 50 g / l. When using such pickling solutions, the result obtained is particularly favorable.
Im Anschluß an eine evtl. Entfernung von Rost, Zunder und Phosphatschichten empfiehlt es sich, die Einzelteile mit einer Lösung in Kontakt zu bringen, die die gleichen Säuren, jedoch in Konzentrationen im Bereich von 0,3 bis 3 Gew.% enthält, und eine Temperatur von lediglich 20 bis 50°C besitzt. Dadurch werden die nach dem Ausheben aus der Beizlösung auf den Metalloberflächen durch Antrocknung gebildeten Metallsalze leicht wieder in Lösung gebracht. Eine erneute Bildung derartiger Antrocknungen aus der sauren Spüllösung wird durch die im Vergleich zum Beizbad deutlich niedrigere Badtemperatur wirksam vermieden.Following a possible removal of rust, scale and phosphate layers, it is advisable to bring the individual parts into contact with a solution which contains the same acids, but in concentrations in the range from 0.3 to 3% by weight, and one Has temperature of only 20 to 50 ° C. As a result, the metal salts formed by drying on the metal surfaces after removal from the pickling solution are easily brought back into solution. A renewed formation of such drying out of the acidic rinsing solution is effectively avoided by the bath temperature, which is significantly lower than in the pickling bath.
Obgleich nicht zwingend erforderlich ist es doch vorteilhaft, die Einzelteile zwecks Ausbildung eines feinkristallinen Phosphatüberzuges in an sich bekannter Weise mit einer Dispersion, die eine wäßrige Aufschlämmung von Titanphosphat darstellt und ggf. zusätzlich kondensierte Phosphate enthält, zu aktivieren.Although not absolutely necessary, it is advantageous to activate the individual parts in order to form a finely crystalline phosphate coating in a manner known per se with a dispersion which is an aqueous slurry of titanium phosphate and, if appropriate, additionally contains condensed phosphates.
Nach der Phosphatierbehandlung wird üblicherweise mit Wasser gespült, ggf. nachgespült und bei Bedarf getrocknet.After the phosphating treatment, it is usually rinsed with water, rinsed if necessary and dried if necessary.
Zum Zweck der Verbesserung des Korrosionsschutzes sieht eine weitere vorteilhafte Ausführungsform der Erfindung vor, die Einzelteile mit einer chromhaltigen oder chromfreien Nachspüllösung zu passivieren. Ggf. kann auch mit einer Emulsion eines Korrosionsschutzöles nachbehandelt werden oder aber mit oder ohne Passivierung eine Lackierung erfolgen. Für den Fall, daß eine Kaltumformung beabsichtigt ist, kann auch eine Nachbehandlung mit einem Seifenbad erfolgen.For the purpose of improving the corrosion protection, a further advantageous embodiment of the invention provides for the individual parts to be passivated with a chrome-containing or chrome-free rinse solution. Possibly. can also be treated with an emulsion of an anti-corrosion oil, or it can be painted with or without passivation. In the event that cold forming is intended, an aftertreatment with a soap bath can also be carried out.
Die nach dem erfindungsgemäßen Verfahren erzeugten Phosphatüberzüge sind auf allen Gebieten, auf denen Phosphatüberzüge Verwendung finden, mit Vorteil einsetzbar. Besonders günstig ist jedoch das erfindungsgemäße Phosphatierverfahren bei der Verbesserung des Korrosionsschutzes im Falle einer anschließenden Lackierung.The phosphate coatings produced by the process according to the invention can be used advantageously in all fields in which phosphate coatings are used. However, the phosphating process according to the invention is particularly favorable in improving the corrosion protection in the case of a subsequent painting.
Die Erfindung wird anhand des nachfolgenden Beispiels beispielsweise und näher erläutert.The invention is illustrated by way of example and in more detail using the example below.
Tiefgezogene Automobilzubehörteile aus Stahl der Qualität C15 wurden wie folgt behandelt:
- Reinigen:
- 69 % NaOH
24 % Natriumglukonat
4 % Na-Hexametaphosphat
3 % Tensid
100 g/l, 90 - 95°C, 10 sec Spritzen - Spülen:
- Heißwasser, 80 - 90°C, 10 sec Tauchen
- Beizen/Entzundern:
- 20 % H₃PO₄, 90 - 95°C,
10 sec Tauchen - Spülen:
- Phosphorsäure 1%, Raumtemperatur, 10 sec Tauchen
- Spülen:
- Frischwasser, Raumtemperatur, 10 sec Tauchen
- Aktivieren:
- 2 g/l Titanphosphat, 40°C, 10 sec Tauchen
- Phosphatieren:
- 44 g/l Zn
6,4 g/l Na
0,05 g/l Ni
0,008 g/l Cu
83 g/l NO₃
38 g/l P₂O₅
1,6 g/l F - Freie Säure:
- 29,5 Punkte
- Gesamtsäure:
- 150 Punkte
- Nitrit:
- 5 Punkte
85°C, 10 sec Tauchen - Spülen:
- Frischwasser, Raumtemperatur, 10 sec Tauchen
- Nachspülen:
- 50°C, 0,1 g/l Cr(VI), 10 sec Tauchen
- Spülen:
- Vollentsalztes Wasser, 10 sec Abbrausen, Raumtemperatur
- Clean:
- 69% NaOH
24% sodium gluconate
4% Na hexametaphosphate
3% surfactant
100 g / l, 90 - 95 ° C, 10 sec spraying - Do the washing up:
- Hot water, 80 - 90 ° C, 10 sec diving
- Pickling / descaling:
- 20% H₃PO₄, 90 - 95 ° C,
10 sec diving - Do the washing up:
- Phosphoric acid 1%, room temperature, 10 sec immersion
- Do the washing up:
- Fresh water, room temperature, 10 sec diving
- Activate:
- 2 g / l titanium phosphate, 40 ° C, 10 sec immersion
- Phosphating:
- 44 g / l Zn
6.4 g / l Na
0.05 g / l Ni
0.008 g / l Cu
83 g / l NO₃
38 g / l P₂O₅
1.6 g / l F - Free acid:
- 29.5 points
- Total acidity:
- 150 points
- Nitrite:
- 5 points
85 ° C, 10 sec diving - Do the washing up:
- Fresh water, room temperature, 10 sec diving
- Rinsing:
- 50 ° C, 0.1 g / l Cr (VI), 10 sec immersion
- Do the washing up:
- Demineralized water, 10 sec spray, room temperature
Der nach diesem Arbeitsgang erzeugte Phosphatüberzug besaß ein Flächengewicht von 4 bis 5 g/m². Der Phosphatüberzug war gleichmäßig deckend und feinkristallin.The phosphate coating produced after this operation had a basis weight of 4 to 5 g / m². The phosphate coating was uniformly opaque and fine crystalline.
Claims (12)
- A process of forming phosphate coatings on individual parts consisting of metal and at least a part of their surfaces consist of iron or steel, wherein aqueous phosphating solutions are employed, which contain zinc ions, phosphate ions, nitrate ions, fluoride ions, nickel ions, copper ions and autocatalytically formed nitrite ions and are virtually free of iron(II) ions, characterized in that the individual parts are contacted at a temperature in the range from 60 to 100°C for 3 to 30 seconds with a phosphating solution which contains
10 to 80 g/l zinc
12 to 80 g/l phosphate (calculated as P₂O₅)
40 to 150 g/l nitrate and, in addition
0.1 to 5 g/l fluoride
0.01 to 10 g/l nickel
0.001 to 0.1 g/l copper
and in which the ratio of free acid to total acid has been adjusted to (0.1 to 0.3):1 and which contains at least 80 points of total acid. - A process according to claim 1, characterized in that the individual parts are contacted with a phosphating solution which contains
30 to 60 g/l zinc
30 to 50 g/l phosphate (calculated as P₂O₅)
65 to 100 g/l nitrate
0.5 to 3,0 g/l fluoride
0.02 to 0.5 g/l nickel and
0.001 to 0.1 g/l copper. - A process according to claim 1 or 2, characterized in that the individual parts are contacted with a phosphating solution which contains additional accelerators.
- A process according to claim 1, 2 or 3, characterized in that the individual parts are contacted with a phosphating solution which additionally contains 0.1 to 10 g/l preferably 1 to 5 g/l, manganese.
- A process according to claim 1, 2, 3 or 4, characterized in that the individual parts are contacted with a phosphating solution which additionally contains 0.05 to 3 g/l tartaric acid and/or citric acid.
- A process according to any of claims 1 to 5, characterized in that the individual parts before being phosphated are cleaned and are optionally treated for a removal of rust, scale and phosphate layers and are activated and when they have been phosphated are passivated with an afterrinse solution and each of said process steps is carried out for 3 to 30 seconds.
- A process according to claim 6, characterized in that the individual parts are cleaned in that they are contacted with an alkaline cleaning solution which is at a temperature in the range between 60 and 100°C and has a concentration in the range from 20 to 200 g/l.
- A process according to claim 6 or 7, characterized in that the individual parts are contacted with a sulfuric acid solution or a phosphoric acid solution which is at a temperature in the range from 60 to 100°C and has a concentration in the range from 5 to 50 % by weight.
- A process according to claim 8, characterized in that the individual parts are contacted with a sulfuric acid solution or a phosphoric acid solution which in addition contains iron(II) and/or iron(III) ions in a concentration in the range from 1 to 50 g/l.
- A process according to claim 8 or 9, characterized in that after the treatment with the sulfuric acid solution or phosphoric acid solution the individual parts are contacted with a solution which contains the same acids in a concentration in the range from 0.3 to 3 % by weight and is at a temperature from 20 to 50°C.
- A process according to any of claims 1 to 10, characterized in that the individual parts are activated with a dispersion which consists of an aqueous slurry of titanium phosphate and optionally contains also condensed phosphates.
- A process according to any of claims 1 to 11, characterized in that the individual parts to which the phosphate coating has been applied are passivated with an afterrinse solution which contains chromium or is free of chromium.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3803068 | 1988-02-03 | ||
| DE3803068 | 1988-02-03 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0327153A2 EP0327153A2 (en) | 1989-08-09 |
| EP0327153A3 EP0327153A3 (en) | 1990-04-25 |
| EP0327153B1 true EP0327153B1 (en) | 1993-08-04 |
Family
ID=6346467
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP89200142A Expired - Lifetime EP0327153B1 (en) | 1988-02-03 | 1989-01-24 | Process for applying phosphate coatings to metals |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4950339A (en) |
| EP (1) | EP0327153B1 (en) |
| JP (1) | JP2713334B2 (en) |
| CA (1) | CA1330515C (en) |
| DE (1) | DE58905074D1 (en) |
| ES (1) | ES2058464T3 (en) |
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| DE3913089A1 (en) * | 1989-04-21 | 1990-10-25 | Henkel Kgaa | CHLORATE- AND NITRITE-FREE METHOD FOR THE PRODUCTION OF NICKEL- AND MANGANE-CONTAINING ZINC PHOSPHATE LAYERS |
| DE4433946A1 (en) * | 1994-09-23 | 1996-03-28 | Henkel Kgaa | Phosphating process without rinsing |
| DE19639597C2 (en) * | 1996-09-26 | 2000-01-20 | Henkel Kgaa | Process for the phosphating of running strips made of cold or hot rolled steel in high-speed conveyor systems |
| US5954892A (en) * | 1998-03-02 | 1999-09-21 | Bulk Chemicals, Inc. | Method and composition for producing zinc phosphate coatings on metal surfaces |
| JP3479609B2 (en) * | 1999-03-02 | 2003-12-15 | 日本パーカライジング株式会社 | Sludge-free zinc phosphate treatment liquid and zinc phosphate treatment method |
| JP4630326B2 (en) * | 1999-08-09 | 2011-02-09 | 新日本製鐵株式会社 | Method for producing phosphate-treated zinc-plated steel sheet with excellent workability |
| JP2001170557A (en) * | 1999-12-21 | 2001-06-26 | Nisshin Steel Co Ltd | Surface treatment liquid for plated steel plate and treating method therefor |
| DE10010355A1 (en) * | 2000-03-07 | 2001-09-13 | Chemetall Gmbh | Applying phosphate coatings to metallic surfaces comprises wetting with an aqueous acidic phosphatizing solution containing zinc ions, manganese ions and phosphate ions, and drying the solution |
| US6530999B2 (en) | 2000-10-10 | 2003-03-11 | Henkel Corporation | Phosphate conversion coating |
| CN100372672C (en) * | 2002-07-31 | 2008-03-05 | 新日本制铁株式会社 | Resin-lined steel pipe and method for production thereof |
| ES2731279T3 (en) | 2013-03-06 | 2019-11-14 | Quaker Chem Corp | High temperature conversion coating on steel and iron substrates |
| CN105603406A (en) * | 2015-12-31 | 2016-05-25 | 芜湖市金宇石化设备有限公司 | Method for preparing treatment fluid for phosphating treatment before coating automobile doors |
| CN105543822A (en) * | 2015-12-31 | 2016-05-04 | 芜湖市金宇石化设备有限公司 | Treatment liquid for phosphating before painting of automobile door |
| CN105463422A (en) * | 2015-12-31 | 2016-04-06 | 芜湖市金宇石化设备有限公司 | Phosphating method before coating automobile doors |
| CN111197163A (en) * | 2018-11-20 | 2020-05-26 | 天津市银丰钢绞线股份有限公司 | Pretreatment process of steel strand |
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- 1989-01-24 EP EP89200142A patent/EP0327153B1/en not_active Expired - Lifetime
- 1989-01-24 ES ES89200142T patent/ES2058464T3/en not_active Expired - Lifetime
- 1989-01-24 DE DE8989200142T patent/DE58905074D1/en not_active Expired - Lifetime
- 1989-02-01 US US07/305,214 patent/US4950339A/en not_active Expired - Fee Related
- 1989-02-01 JP JP1020980A patent/JP2713334B2/en not_active Expired - Lifetime
- 1989-02-02 CA CA000589900A patent/CA1330515C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| DE58905074D1 (en) | 1993-09-09 |
| US4950339A (en) | 1990-08-21 |
| CA1330515C (en) | 1994-07-05 |
| EP0327153A2 (en) | 1989-08-09 |
| EP0327153A3 (en) | 1990-04-25 |
| JPH01259180A (en) | 1989-10-16 |
| JP2713334B2 (en) | 1998-02-16 |
| ES2058464T3 (en) | 1994-11-01 |
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