EP0304108B1 - Metal-phosphating process - Google Patents
Metal-phosphating process Download PDFInfo
- Publication number
- EP0304108B1 EP0304108B1 EP88201613A EP88201613A EP0304108B1 EP 0304108 B1 EP0304108 B1 EP 0304108B1 EP 88201613 A EP88201613 A EP 88201613A EP 88201613 A EP88201613 A EP 88201613A EP 0304108 B1 EP0304108 B1 EP 0304108B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- phosphating
- contain
- aluminum
- zinc
- fluoride
- 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
Links
- 238000000034 method Methods 0.000 title claims description 26
- 229910052782 aluminium Inorganic materials 0.000 claims description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 19
- 239000011701 zinc Substances 0.000 claims description 17
- 229910052725 zinc Inorganic materials 0.000 claims description 17
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 16
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
- 229910001335 Galvanized steel Inorganic materials 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- 239000008397 galvanized steel Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 238000010422 painting Methods 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 5
- 239000007800 oxidant agent Substances 0.000 claims description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 4
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 claims description 4
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 claims description 4
- IJPPOBHVBIMQFD-UHFFFAOYSA-K magnesium;zinc;phosphate Chemical compound [Mg+2].[Zn+2].[O-]P([O-])([O-])=O IJPPOBHVBIMQFD-UHFFFAOYSA-K 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 3
- 150000002978 peroxides Chemical class 0.000 claims description 3
- UJJUJHTVDYXQON-UHFFFAOYSA-N nitro benzenesulfonate Chemical compound [O-][N+](=O)OS(=O)(=O)C1=CC=CC=C1 UJJUJHTVDYXQON-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 description 13
- 235000021317 phosphate Nutrition 0.000 description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 12
- 239000010452 phosphate Substances 0.000 description 12
- 238000007654 immersion Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000003973 paint Substances 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000006253 efflorescence Methods 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 206010037844 rash Diseases 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- QMGZHIPTCWRMAK-UHFFFAOYSA-N Cl(=O)(=O)O.N(=O)O.[N+](=O)(O)[O-] Chemical compound Cl(=O)(=O)O.N(=O)O.[N+](=O)(O)[O-] QMGZHIPTCWRMAK-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910017665 NH4HF2 Inorganic materials 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- NPMCMPGGJVXBDP-UHFFFAOYSA-N [N+](=O)(O)[O-].Br(=O)(=O)O Chemical compound [N+](=O)(O)[O-].Br(=O)(=O)O NPMCMPGGJVXBDP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- HUQUQWWXYHDBHK-UHFFFAOYSA-N chloric acid;nitric acid;2-nitrobenzenesulfonic acid Chemical compound O[N+]([O-])=O.OCl(=O)=O.OS(=O)(=O)C1=CC=CC=C1[N+]([O-])=O HUQUQWWXYHDBHK-UHFFFAOYSA-N 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 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
- -1 moisture Chemical class 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- YBVAXJOZZAJCLA-UHFFFAOYSA-N nitric acid nitrous acid Chemical compound ON=O.O[N+]([O-])=O YBVAXJOZZAJCLA-UHFFFAOYSA-N 0.000 description 1
- OCENVHJSOPHHHH-UHFFFAOYSA-N nitric acid;2-nitrobenzenesulfonic acid Chemical compound O[N+]([O-])=O.OS(=O)(=O)C1=CC=CC=C1[N+]([O-])=O OCENVHJSOPHHHH-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052827 phosphophyllite Inorganic materials 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000000007 visual effect Effects 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
- C23C22/07—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
- C23C22/34—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
- C23C22/368—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 magnesium cations
Definitions
- the invention relates to a method for phosphating galvanized steel, optionally together with additionally present aluminum, before painting with phosphating solutions based on zinc magnesium phosphate.
- the object of the invention is to provide a process for the phosphating of galvanized steel, optionally together with additionally present aluminum, as a pretreatment for the coating, which does not have the aforementioned disadvantages, but rather makes it possible to produce uniform phosphate layers on the metals which are outstanding as Are suitable for painting.
- galvanized steel is understood to mean steel which, for example, on the hot-dip path or in the electrolytic process with zinc or zinc alloy coatings e.g. Pure zinc, zinc nickel, zinc iron, zinc aluminum was coated.
- zinc or zinc alloy coatings e.g. Pure zinc, zinc nickel, zinc iron, zinc aluminum was coated.
- aluminum in the sense of the invention includes Pure aluminum and alloys of aluminum with magnesium, zinc, copper, silicon, manganese etc.
- the concentration of fluoride detected with the fluoride-sensitive electrode corresponds approximately to that in the Phosphating solution present proportion of dissociated fluoride (F ⁇ ).
- F (el) value 80 to 400 mg / l at the usual phosphating bath pH values of the baths, about 0.4 to 0.9 g / l NH4HF2 or equivalent amounts of other single fluoride-containing compounds must be added will.
- the bath is preferably supplemented by adding enough fluoride-containing compound to the phosphating bath until the desired measured value of F (el) is reached.
- the metal surfaces to be treated must be free from disruptive deposits of oils, lubricants, oxides and the like, which can impair proper layer formation.
- the surfaces are cleaned in a suitable manner.
- the surface is preferably coated with an activating agent known per se, e.g. an aqueous suspension containing titanium phosphate, activated.
- the activating agent can be used in the cleaning bath or as a separate process step.
- the phosphating solutions according to the invention are used in spraying, spray-immersion or immersion at temperatures between 40 and 60 ° C.
- the times during which the metal surfaces are brought into contact with the phosphating solution to form a covering phosphate layer are in the case of galvanized steel, e.g. between 20 sec and 10 min, for aluminum e.g. between 1 and 10 min.
- the cations zinc, magnesium and nickel are in the Phosphating solution introduced, for example, as metal, oxide, carbonate, phosphate, nitrate, chloride and / or complex fluoride.
- the phosphate portion is fed to the solution via phosphates and / or phosphoric acid.
- additional cations for example Na, K, NH4 or anions, for example nitrate, chloride, sulfate, are used.
- the value of the free acid (total acid) is identical to the consumption of ml 0.1 n NaOH for neutralizing a 10 ml bath sample against the first turning point (second turning point) of the phosphoric acid.
- the phosphating bath also contains at least one oxidizing agent from the group consisting of nitrate, nitrite, chlorate, bromate, peroxide and nitrobene sulfonate, e.g. the following quantities can be used: 2 to 20 g / l nitrate; 0.05 to 0.5 g / l nitrite; 0.5 to 5 g / l chlorate; 0.2 to 3 g / l bromate; 0.02 to 0.1 g / l peroxide; 0.1 to 1 g / l nitrobenzenesulfonate.
- the oxidizing agents can also be combined with one another, e.g. Nitrate nitrite, (nitrate) chlorate nitrite, nitrate bromate, (nitrate) chlorate nitrobenzenesulfonate, nitrate nitrobenzenesulfonate.
- the three components chloride and / or Bromide), (nitrate) and (nickel) only two each in a concentration of more than 0.1 g / l, while the third may only be present in a maximum concentration of 0.1 g / l.
- Chloride and bromide are counted as one component and their individual concentrations are added. Chloride can, for example, get into the phosphating bath from the preparation water for the phosphating solution and / or as a reduction product of chlorate.
- the bromate accelerator in particular should be regarded as the source.
- the phosphating bath preferably contains simple and / or complex fluoride.
- the group of suitable complex fluorides includes e.g. Fluoroborates and fluorosilicates.
- the phosphating solutions used in the process according to the invention can also contain further additives, but mostly in minor amounts. These include Copper, manganese, calcium, iron, cobalt, polyphosphates, polyhydroxycarboxylic acids, surfactants and agents for influencing the sludge separation.
- the phosphate layers produced according to the invention are used as preparation for a subsequent painting. They are preferably used for workpieces which are subsequently electrocoated, in particular cathodically electrocoated. In this way you get layers of paint, which are characterized by a high resistance to infiltration when exposed to corrosion, e.g. due to normal outdoor weathering, outdoor weathering accelerated with salt, moisture, salt spray and wash liquor, and have very good adhesion to scratching and impact stress before and after corrosion.
- the method according to the invention is particularly suitable for the pretreatment of housings for household appliances and technical apparatus, of metal furniture, of vehicle bodies and of vehicle accessories before painting.
- Sheets made of steel, electrolytically galvanized steel, hot-dip galvanized steel and AlMgSi were treated after alkaline cleaning, water rinsing and activation in an aqueous titanium phosphate suspension with the phosphating solutions listed in the table at 50 ° C for 2 minutes by spraying or 3 minutes by immersion. This was followed by rinsing with water, an aqueous passivating solution containing chromium (VI), demineralized water and a drying stage.
- VI chromium
- the table shows that flawless layers could be obtained on galvanized steel throughout the work area, with the exception of the cases in which nitrate, chloride and nickel were present in a concentration of more than 0.1 g / l each (Examples 6 and 11), insofar as the ranges essential to the invention were taken into account for the Zn, Mg and Ni concentration. Crystalline, uniform layer formation was always achieved on AlMgSi when the fluoride concentration F (el) measured electrometrically with a fluorine-sensitive electrode was in the range between 80 to 400 mg / l (Examples 4 to 6 and 13 to 20).
- the layers were provided with a cathodic electrodeposition paint and an automotive paint structure and subjected to the usual technical tests. In all cases where crystalline layers were present on the metal substrate, excellent test results were achieved.
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Description
Die Erfindung betrifft ein Verfahren zur Phosphatierung von verzinktem Stahl, gegebenenfalls gemeinsam mit zusätzlich vorhandenem Aluminium, vor der Lackierung mit Phosphatierlösungen auf Basis Zinkmagnesiumphosphat.The invention relates to a method for phosphating galvanized steel, optionally together with additionally present aluminum, before painting with phosphating solutions based on zinc magnesium phosphate.
Es ist bekannt, Metalle mit Zinkmagnesiumphosphatlösung zu behandeln und auf diese Weise Phosphatschichten auf ihnen abzuscheiden. Ferner gehört es zum Stand der Technik, insbesondere vor der Lackierung Niedrigzinkphosphatierverfahren einzusetzen, weil diese auf Stahl Phosphatschichten mit einem hohen Phosphophyllitanteil erzeugen, der sich günstig auf Lackhaftung und Unterwanderungsbeständigkeit des Lackfilms bei Korrosionsbeanspruchung auswirkt.It is known to treat metals with zinc magnesium phosphate solution and in this way to deposit phosphate layers on them. Furthermore, it is part of the prior art to use low-zinc phosphating processes, in particular before painting, because these produce phosphate layers on steel with a high proportion of phosphophyllite, which has a favorable effect on paint adhesion and resistance to infiltration of the paint film when exposed to corrosion.
Die bekannten Verfahren weisen jedoch in verschiedener Hinsicht Nachteile auf. So ist die Schichtbildung auf Zink in Phosphatierbädern, die nur Zn und Mg als zweiwertige Kationen enthalten, vielfach ungenügend. Nickelhaltige Niedrigzink-Phosphatierbäder liefern zwar visuell einwandfreie Phosphatschichten auf Stahl und Zink, jedoch ist die Haftung von Lackfilmen auf Zink bei Feuchteeinwirkung oft nicht ausreichend. Ferner treten insbesondere bei der Anwendung im Tauchverfahren häufig Oberflächenstörungen in der Phosphatschicht auf Zink auf, die auf lokale kristalline Ausblühungen, auch Stippen genannt, zurückzuführen sind, und die die Ausbildung eines gleichmäßigen Lackfilmes stören. Außerdem bereitet die Erzeugung kristalliner Phosphatschichten auf Aluminium aus Bädern auf Basis Zinkmagnesiumphosphat Schwierigkeiten.However, the known methods have disadvantages in various respects. The formation of layers on zinc in phosphating baths which contain only Zn and Mg as divalent cations is often insufficient. Nickel-containing low-zinc phosphating baths provide visually perfect phosphate layers on steel and zinc, but the adhesion of paint films to zinc is often not sufficient when exposed to moisture. In addition, surface defects in the phosphate layer on zinc, which are due to local crystalline efflorescence, also called specks, and which disrupt the formation of a uniform lacquer film, frequently occur, especially when used in the dipping process. In addition, the Generation of crystalline phosphate layers on aluminum from baths based on zinc magnesium phosphate difficulties.
Aufgabe der Erfindung ist es, ein Verfahren zur Phosphatierung von verzinktem Stahl, gegebenenfalls gemeinsam mit zusätzlich vorhandenem Aluminium, als Vorbehandlung für die Lackierung bereitzustellen, das die vorgenannten Nachteile nicht aufweist, sondern es ermöglicht, auf den Metallen gleichmäßige Phosphatschichten zu erzeugen, die hervorragend als Basis für eine Lackierung geeignet sind.The object of the invention is to provide a process for the phosphating of galvanized steel, optionally together with additionally present aluminum, as a pretreatment for the coating, which does not have the aforementioned disadvantages, but rather makes it possible to produce uniform phosphate layers on the metals which are outstanding as Are suitable for painting.
Die Aufgabe wird gelöst, indem das Verfahren der eingangs genannten Art entsprechend der Erfindung derart ausgestaltet wird, daß man die Metalloberflächen bei einer Temperatur zwischen 40 und 60°C mit wässrigen Phosphatierlösungen in Berührung bringt, die
0,4 bis 5,0 g/l Mg
0,05 bis 2,0 g/l Ni
8 bis 20 g/l P₂O₅
und mindestens ein Oxidationsmittel enthalten, in denen das Verhältnis von Freier Säure zu Gesamtsäure (0,02 bis 0,15):1 beträgt, mit der Maßgabe, daß
- a) bei Abwesenheit von Aluminium die Zinkkonzentration der Phosphatierlösungen im Spritzverfahren auf einen Wert im Bereich von 0,4 und 1,0 g/l und im Spritz-Tauch- und Tauchverfahren auf einen Wert im Bereich von 0,9 und 1,5 g/l
- b) bei Anwesenheit von Aluminium die Zinkkonzentration der Phosphatierlösungen im Spritzverfahren auf einen Wert im Bereich von 0,7 und 1,0 g/l und im Spritz-Tauch- und Tauchverfahren auf einen Wert im Bereich von 1,4 und 2,0 g/l eingestellt wird und zusätzlich einen Gehalt von 80 bis 400 mg/l Fluorid ("F(el)", bestimmt durch eine in die Badlösung eingetauchte fluoridsensitive Elektrode) aufweist.
0.4 to 5.0 g / l Mg
0.05 to 2.0 g / l Ni
8 to 20 g / l P₂O₅
and contain at least one oxidizing agent in which the ratio of free acid to total acid is (0.02 to 0.15): 1, with the proviso that
- a) in the absence of aluminum, the zinc concentration of the phosphating solutions in the spray process to a value in the range of 0.4 and 1.0 g / l and in the spray-immersion and immersion process to a value in the range of 0.9 and 1.5 g / l
- b) in the presence of aluminum, the zinc concentration of the phosphating solutions in the spray process to a value in the range from 0.7 and 1.0 g / l and in the spray-immersion and immersion process to a value in the range from 1.4 and 2.0 g / l is set and additionally has a content of 80 to 400 mg / l fluoride ("F (el)", determined by a fluoride-sensitive electrode immersed in the bath solution).
Unter dem Begriff verzinkter Stahl ist im Rahmen der Erfindung Stahl zu verstehen, der mit einem geeigneten Verfahren z.B. auf dem Schmelztauchwege oder im elektrolytischen Prozeß mit Zink- bzw. Zinklegierungsüberzügen z.B. Rein-Zink, Zink-Nickel, Zink-Eisen, Zink-Aluminium überzogen wurde. Unter den Begriff Aluminium im Sinne der Erfindung fallen u.a. Rein-Aluminium sowie Legierungen des Aluminium mit Magnesium, Zink, Kupfer, Silicium, Mangan etc.In the context of the invention, the term galvanized steel is understood to mean steel which, for example, on the hot-dip path or in the electrolytic process with zinc or zinc alloy coatings e.g. Pure zinc, zinc nickel, zinc iron, zinc aluminum was coated. The term aluminum in the sense of the invention includes Pure aluminum and alloys of aluminum with magnesium, zinc, copper, silicon, manganese etc.
Das Merkmal, wonach bei zusätzlich vorhandenem Aluminium die Lösungen einen Gehalt von 80 bis 400 mg/l Fluorid aufweisen müssen, bringt zum Ausdruck, daß eine derartige Fluoridkonzentration bei Anwesenheit von Aluminium unerläßlich ist. Andernfalls ist eine kristalline Schichtausbildung auf Aluminium nicht möglich. Das bedeutet nicht, daß bei Abwesenheit von Aluminium die Lösungen nicht auch Fluorid enthalten können.The feature, according to which the solutions must have a content of 80 to 400 mg / l fluoride in the presence of aluminum, indicates that such a fluoride concentration is essential in the presence of aluminum. Otherwise a crystalline layer formation on aluminum is not possible. This does not mean that the solutions cannot contain fluoride in the absence of aluminum.
Die mit der fluoridsensitiven Elektrode erfaßte Konzentration an Fluorid entspricht etwa dem in der Phosphatierlösung vorliegendem Anteil an dissoziiertem Fluorid (F⁻). Um einen F(el)-Wert von 80 bis 400 mg/l bei den üblichen Phosphatierbad-pH-Werten der Bäder einzustellen, müssen etwa 0,4 bis 0,9 g/l NH₄HF₂ oder äquivalente Mengen anderer Einfach-Fluorid enthaltender Verbindungen zugegeben werden. Die Badergänzung erfolgt vorzugsweise so, daß man dem Phosphatierbad so viel Einfach-Fluorid enthaltende Verbindung zusetzt, bis der gewünschte Meßwert von F(el) erreicht ist.The concentration of fluoride detected with the fluoride-sensitive electrode corresponds approximately to that in the Phosphating solution present proportion of dissociated fluoride (F⁻). In order to set an F (el) value of 80 to 400 mg / l at the usual phosphating bath pH values of the baths, about 0.4 to 0.9 g / l NH₄HF₂ or equivalent amounts of other single fluoride-containing compounds must be added will. The bath is preferably supplemented by adding enough fluoride-containing compound to the phosphating bath until the desired measured value of F (el) is reached.
Die zu behandelnden Metalloberflächen müssen frei sein von störenden Belägen aus Ölen, Schmierstoffen, Oxiden und dergleichen, die eine einwandfreie Schichtbildung beeinträchtigen können. Hierzu werden die Oberflächen in geeigneter Weise gereinigt. Zur Unterstützung der Phosphatschichtbildung wird die Oberfläche vorzugsweise vor der Erzeugung des Phosphatüberzuges mit einem an sich bekannten Aktivierungsmittel, z.B. einer titanphosphathaltigen wässrigen Suspension, aktiviert. Das Aktivierungsmittel kann im Reinigerbad oder als getrennte Verfahrensstufe zum Einsatz kommen.The metal surfaces to be treated must be free from disruptive deposits of oils, lubricants, oxides and the like, which can impair proper layer formation. For this purpose, the surfaces are cleaned in a suitable manner. To support the formation of the phosphate layer, the surface is preferably coated with an activating agent known per se, e.g. an aqueous suspension containing titanium phosphate, activated. The activating agent can be used in the cleaning bath or as a separate process step.
Die erfindungsgemäßen Phosphatierlösungen werden im Spritzen, Spritz-Tauchen oder Tauchen bei Temperaturen zwischen 40 und 60°C eingesetzt. Die Zeiten, während der die Metalloberflächen mit der Phosphatierlösung zur Ausbildung einer deckenden Phosphatschicht in Berührung gebracht werden, liegen bei verzinktem Stahl z.B. zwischen 20 sec und 10 min, bei Aluminium z.B. zwischen 1 und 10 min.The phosphating solutions according to the invention are used in spraying, spray-immersion or immersion at temperatures between 40 and 60 ° C. The times during which the metal surfaces are brought into contact with the phosphating solution to form a covering phosphate layer are in the case of galvanized steel, e.g. between 20 sec and 10 min, for aluminum e.g. between 1 and 10 min.
Die Kationen Zink, Magnesium und Nickel werden in die Phosphatierlösung z.B. als Metall, Oxid, Carbonat, Phosphat, Nitrat, Chlorid und/oder komplexes Fluorid eingebracht. Der Phosphatanteil wird über Phosphate und/oder Phosphorsäure der Lösung zugeführt. Zur Einstellung des gewünschten Verhältnisses von Freier Säure zur Gesamtsäure von (0,02 bis 0,15):1 werden weitere Kationen, z.B. Na, K, NH₄ oder Anionen, z.B. Nitrat, Chlorid, Sulfat mit verwendet.The cations zinc, magnesium and nickel are in the Phosphating solution introduced, for example, as metal, oxide, carbonate, phosphate, nitrate, chloride and / or complex fluoride. The phosphate portion is fed to the solution via phosphates and / or phosphoric acid. To set the desired ratio of free acid to total acid from (0.02 to 0.15): 1, additional cations, for example Na, K, NH₄ or anions, for example nitrate, chloride, sulfate, are used.
Der Wert der Freien Säure (Gesamtsäure) ist identisch mit dem Verbrauch an ml 0,1 n NaOH zur Neutralisation einer 10 ml Badprobe gegen den ersten Wendepunkt (zweiten Wendepunkt) der Phosphorsäure.The value of the free acid (total acid) is identical to the consumption of ml 0.1 n NaOH for neutralizing a 10 ml bath sample against the first turning point (second turning point) of the phosphoric acid.
Das Phosphatierbad enthält außerdem mindestens ein Oxidationsmittel aus der Gruppe Nitrat, Nitrit, Chlorat, Bromat, Peroxid und Nitrobensulfonat, wobei z.B. folgende Mengen zur Anwendung kommen können: 2 bis 20 g/l Nitrat; 0,05 bis 0,5 g/l Nitrit; 0,5 bis 5 g/l Chlorat; 0,2 bis 3 g/l Bromat; 0,02 bis 0,1 g/l Peroxid; 0,1 bis 1 g/l Nitrobenzolsulfonat. Die Oxidationsmittel können auch miteinander kombiniert werden, so z.B. Nitrat-Nitrit, (Nitrat-)Chlorat-Nitrit, Nitrat-Bromat, (Nitrat-)Chlorat-Nitrobenzolsulfonat, Nitrat-Nitrobenzolsulfonat.The phosphating bath also contains at least one oxidizing agent from the group consisting of nitrate, nitrite, chlorate, bromate, peroxide and nitrobene sulfonate, e.g. the following quantities can be used: 2 to 20 g / l nitrate; 0.05 to 0.5 g / l nitrite; 0.5 to 5 g / l chlorate; 0.2 to 3 g / l bromate; 0.02 to 0.1 g / l peroxide; 0.1 to 1 g / l nitrobenzenesulfonate. The oxidizing agents can also be combined with one another, e.g. Nitrate nitrite, (nitrate) chlorate nitrite, nitrate bromate, (nitrate) chlorate nitrobenzenesulfonate, nitrate nitrobenzenesulfonate.
Um bei der Phosphatierung von verzinktem Stahl die Ausbildung von kleinen punktförmigen Kristallausblühungen (Stippen) auf der Phosphatschicht, insbesondere bei der Anwendung im Spritz-Tauch- und Tauchverfahren zu vermeiden, dürfen in einer speziellen Ausgestaltung der Erfindung von den drei Komponenten (Chlorid und/oder Bromid), (Nitrat) und (Nickel) nur je zwei in einer Konzentration von je über 0,1 g/l zugegen sein, während die jeweils dritte nur in einer Maximalkonzentration von 0,1 g/l vorliegen darf. Chlorid und Bromid werden hierbei als eine Komponente gezählt und ihre Einzelkonzentrationen addiert. Chlorid kann z.B. aus dem Ansatzwasser für die Phosphatierlösung und/oder als Reduktionsprodukt von Chlorat in das Phosphatierbad gelangen. Im Falle des Bromid ist insbesondere der Bromatbeschleuniger als Quelle anzusehen.In order to avoid the formation of small punctiform crystal efflorescences (specks) on the phosphate layer during the phosphating of galvanized steel, in particular when used in the spray-immersion and immersion process, the three components (chloride and / or Bromide), (nitrate) and (nickel) only two each in a concentration of more than 0.1 g / l, while the third may only be present in a maximum concentration of 0.1 g / l. Chloride and bromide are counted as one component and their individual concentrations are added. Chloride can, for example, get into the phosphating bath from the preparation water for the phosphating solution and / or as a reduction product of chlorate. In the case of bromide, the bromate accelerator in particular should be regarded as the source.
Zur Unterstützung der Schichtbildung auf aluminiumhaltigen Zinküberzügen enthält das Phosphatierbad vorzugsweise einfaches und/oder komplexes Fluorid. Zur Gruppe der geeigneten komplexen Fluoride zählen z.B. Fluoroborate und Fluorosilikate.To support the layer formation on aluminum-containing zinc coatings, the phosphating bath preferably contains simple and / or complex fluoride. The group of suitable complex fluorides includes e.g. Fluoroborates and fluorosilicates.
Die im erfindungsgemäßen Verfahren zum Einsatz kommenden Phosphatierlösungen können außer den beschriebenen Komponenten noch weitere Zusätze, meist jedoch in untergeordneten Mengen, enthalten. Hierzu zählen u.a. Kupfer, Mangan, Calcium, Eisen, Kobalt, Polyphosphate, Polyhydroxicarbonsäuren, Tenside sowie Mittel zur Beeinflussung der Schlammabscheidung.In addition to the components described, the phosphating solutions used in the process according to the invention can also contain further additives, but mostly in minor amounts. These include Copper, manganese, calcium, iron, cobalt, polyphosphates, polyhydroxycarboxylic acids, surfactants and agents for influencing the sludge separation.
Die nach der Erfindung erzeugten Phosphatschichten werden als Vorbereitung für eine nachfolgende Lackierung eingesetzt. Vorzugsweise werden sie für Werkstücke angewendet, die anschließend elektrotauchlackiert, insbesondere kathodisch elektrotauchlackiert werden. Man erhält auf diese Weise Lackschichten, die sich durch eine hohe Unterwanderungsbeständigkeit bei Korrosionsbeanspruchung, z.B. durch normale Freibewitterung, durch mit Salz beschleunigte Freibewitterung, durch Feuchtigkeit, durch Salznebel und Waschlauge auszeichnen und eine sehr gute Haftung bei Kratz- und Schlagbeanspruchung vor und nach Korrosionsbelastung aufweisen.The phosphate layers produced according to the invention are used as preparation for a subsequent painting. They are preferably used for workpieces which are subsequently electrocoated, in particular cathodically electrocoated. In this way you get layers of paint, which are characterized by a high resistance to infiltration when exposed to corrosion, e.g. due to normal outdoor weathering, outdoor weathering accelerated with salt, moisture, salt spray and wash liquor, and have very good adhesion to scratching and impact stress before and after corrosion.
Das erfindungsgemäße Verfahren eignet sich insbesondere für die Vorbehandlung von Gehäusen für Haushaltsgeräte und technische Apparate, von Metallmöbeln, von Fahrzeugkarosserien und von Fahrzeugzubehörteilen vor der Lackierung.The method according to the invention is particularly suitable for the pretreatment of housings for household appliances and technical apparatus, of metal furniture, of vehicle bodies and of vehicle accessories before painting.
Das erfindungsgemäße Verfahren wird anhand der folgenden Beispiele beispielsweise und näher erläutert.The process according to the invention is explained, for example and in more detail, using the following examples.
Bleche aus Stahl, elektrolytisch verzinktem Stahl, feuerverzinktem Stahl und AlMgSi wurden nach alkalischer Reinigung, Wasserspülung und Aktivierung in einer wässrigen Titanphosphatsuspension mit den in der Tabelle aufgeführten Phosphatierlösungen bei 50°C 2 min im Spritzen bzw. 3 min im Tauchen behandelt. Hieran schlossen sich Spülungen mit Wasser, Chrom(VI)-haltiger wässriger Passivierlösung, vollentsalztem Wasser sowie eine Trocknungsstufe an.Sheets made of steel, electrolytically galvanized steel, hot-dip galvanized steel and AlMgSi were treated after alkaline cleaning, water rinsing and activation in an aqueous titanium phosphate suspension with the phosphating solutions listed in the table at 50 ° C for 2 minutes by spraying or 3 minutes by immersion. This was followed by rinsing with water, an aqueous passivating solution containing chromium (VI), demineralized water and a drying stage.
Aus der Tabelle ist ersichtlich, daß auf verzinktem Stahl im gesamten Arbeitsbereich einwandfreie Schichten zu erhalten waren, mit Ausnahme der Fälle, in denen Nitrat, Chlorid und Nickel in einer Konzentration von über je 0,1 g/l vorlagen (Beispiele 6 und 11), soweit die erfindungswesentlichen Bereiche für die Zn-, Mg- und Ni-Konzentration beachtet wurden. Auf AlMgSi wurde immer dann eine kristalline, gleichmäßige Schichtbildung erzielt, wenn die elektrometrisch mit einer fluorsensitiven Elektrode gemessene Fluoridkonzentration F(el) im Bereich zwischen 80 bis 400 mg/l lag (Beispiele 4 bis 6 und 13 bis 20).The table shows that flawless layers could be obtained on galvanized steel throughout the work area, with the exception of the cases in which nitrate, chloride and nickel were present in a concentration of more than 0.1 g / l each (Examples 6 and 11), insofar as the ranges essential to the invention were taken into account for the Zn, Mg and Ni concentration. Crystalline, uniform layer formation was always achieved on AlMgSi when the fluoride concentration F (el) measured electrometrically with a fluorine-sensitive electrode was in the range between 80 to 400 mg / l (Examples 4 to 6 and 13 to 20).
Nach visueller Beurteilung wurden die Schichten mit einem kathodischen Elektrotauchlack und einem Automobillackaufbau versehen und den üblichen anwendungstechnischen Prüfungen unterworfen. In allen Fällen, in denen kristalline Schichten auf dem Metallsubstrat vorlagen, wurden ausgezeichnete Prüfergebnisse erzielt.
Claims (5)
- A process for phosphating galvanized steel, optionally together with aluminum which is additionally present, prior to painting, wherein phosphating solutions based on zinc-magnesium phosphate are employed, characterized in that the metal surfaces are contacted at a temperature between 40 and 60°C with aqueous phosphating solutions which contain
0.4 to 5.0 g/l Mg
0.05 to 2.0 g/l Ni
8 to 20 g/l P₂O₅
and at least one oxidizing agent and wherein the ratio of free acid to total acid is (0.02 to 0.15) : 1, provided thata) in the absence of aluminum the zinc concentration of the phosphating solution is adjusted to a value in the range of 0.4 to 1.0 g/l when applied in a spraying process and to a value in the range of 0.9 to 1.5 g/l when applied in a spraying-dipping or dipping processb) in the presence of aluminum the zinc concentration of the phosphating solution is adjusted to a value in the range of 0.7 to 1.0 g/l when applied in a spraying process and to a value in the range of 1.4 to 2.0 g/l when applied in a spraying-dipping or dipping process, and that the phosphating solutions contain additionally 80 to 400 mg/l fluoride "F(el)" as determined with a fluoride-sensitive electrode which is immersed into the bath solution. - A process according to claim 1, characterized in that the metallic surfaces are contacted with phosphating solutions which contain nitrate, nitrite, chlorate, bromate, peroxide and/or nitrobenzene sulfonate as an oxidizing agent.
- A process according to claim 1 or 2, characterized in that the metallic surfaces are contacted with phosphating solutions which contain the three components consisting of (chloride and/or bromide), nitrate and nickel, at least one present in a concentration not exceeding 0,1 g/l.
- A process according to claim 1, 2 or 3, characterized in that the metallic surfaces are contacted with phosphating solutions which contain simple or complex fluoride.
- A process according to one or more of the claims 1 to 4, characterized in that the phosphated workpieces are subsequently electro-dipcoated, preferably cathodically electro-dipcoated.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3727613 | 1987-08-19 | ||
| DE3727613 | 1987-08-19 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0304108A1 EP0304108A1 (en) | 1989-02-22 |
| EP0304108B1 true EP0304108B1 (en) | 1992-05-13 |
Family
ID=6334038
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP88201613A Expired - Lifetime EP0304108B1 (en) | 1987-08-19 | 1988-07-26 | Metal-phosphating process |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0304108B1 (en) |
| JP (1) | JP2680618B2 (en) |
| CA (1) | CA1333147C (en) |
| DE (1) | DE3871031D1 (en) |
| ES (1) | ES2036666T3 (en) |
| GB (1) | GB2208876B (en) |
| ZA (1) | ZA886167B (en) |
Families Citing this family (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3828676A1 (en) * | 1988-08-24 | 1990-03-01 | Metallgesellschaft Ag | PHOSPHATING PROCESS |
| JPH03107469A (en) * | 1989-09-21 | 1991-05-07 | Nippon Parkerizing Co Ltd | Zinc plated material having phosphate chemical conversion coating film excellent in bare corrosion resistance |
| KR100197145B1 (en) * | 1989-12-19 | 1999-06-15 | 후지이 히로시 | Method for phosphating metal surface with zinc phosphate |
| JP2695963B2 (en) * | 1990-03-16 | 1998-01-14 | マツダ株式会社 | Phosphating of metal surfaces |
| DE4131382A1 (en) * | 1990-09-21 | 1992-03-26 | Kobe Steel Ltd | Surface treated aluminium@ alloy sheet for motor car construction - used in making decorative coloured items, zinc phosphate layer having fine grained structure of uniform thickness |
| US5144611A (en) * | 1990-10-01 | 1992-09-01 | International Business Machines Corporation | Optical disk drive cleaner cartridge |
| US5454882A (en) * | 1992-01-13 | 1995-10-03 | Henkel Corporation | Process for controlling a fluoride containing conversion coating forming composition during its use for conversion coating aluminum containing metal |
| JP3181658B2 (en) * | 1992-01-13 | 2001-07-03 | 日本パーカライジング株式会社 | Determination method of effective fluorine concentration in acid chemical conversion treatment of metallic materials |
| JPH05306497A (en) | 1992-04-30 | 1993-11-19 | Nippondenso Co Ltd | Phophatizing chemical conversion treatment |
| DE4306446A1 (en) * | 1993-03-02 | 1994-09-08 | Metallgesellschaft Ag | Procedures to facilitate cold forming |
| JPH07173643A (en) * | 1993-12-21 | 1995-07-11 | Mazda Motor Corp | Method for phosphating metal surface and phosphating solution |
| US5478413A (en) * | 1994-12-27 | 1995-12-26 | Sermatech International, Inc. | Environmentally friendly coating compositions |
| US5797987A (en) * | 1995-12-14 | 1998-08-25 | Ppg Industries, Inc. | Zinc phosphate conversion coating compositions and process |
| DE19606018A1 (en) * | 1996-02-19 | 1997-08-21 | Henkel Kgaa | Zinc phosphating with low levels of nickel and / or cobalt |
| US6413588B1 (en) | 1999-01-11 | 2002-07-02 | E. I. Du Pont De Nemours And Company | Method of producing durable layered coatings |
| DE19921135A1 (en) * | 1999-05-07 | 2000-11-09 | Henkel Kgaa | Process for low-zinc zinc phosphating followed by water treatment |
| JP4658339B2 (en) * | 2001-01-17 | 2011-03-23 | 日本ペイント株式会社 | Metal surface treatment method |
| DE102005059314B4 (en) * | 2005-12-09 | 2018-11-22 | Henkel Ag & Co. Kgaa | Acid, chromium-free aqueous solution, its concentrate, and a process for the corrosion protection treatment of metal surfaces |
| JP5119864B2 (en) * | 2006-10-31 | 2013-01-16 | Ｊｆｅスチール株式会社 | Phosphate-treated galvanized steel sheet and method for producing the same |
| JP4992385B2 (en) * | 2006-10-31 | 2012-08-08 | Ｊｆｅスチール株式会社 | Organic resin-coated phosphate-treated zinc-based plated steel sheet and method for producing the same |
| KR101106516B1 (en) | 2006-10-31 | 2012-01-20 | 제이에프이 스틸 가부시키가이샤 | Phosphate-treated galvanized steel sheet and method for producing the same |
| JP2007314888A (en) * | 2007-07-17 | 2007-12-06 | Toyota Motor Corp | Multilayer coating film structure |
| ES2397997B1 (en) * | 2010-03-22 | 2014-01-17 | Roberto Ruiz Sanz | DEPOSIT BY PASS FOR COMPRESSED AIR. |
| CN102430506A (en) * | 2011-12-15 | 2012-05-02 | 江苏腾奇电力设备科技有限公司 | Paint coating process for radiator cast |
| KR101830508B1 (en) * | 2016-06-24 | 2018-02-21 | 주식회사 포스코 | Phosphate-treated zinc-based plated steel sheet having excellent discoloration resistance and film adhesiveness |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB648888A (en) * | 1947-04-25 | 1951-01-17 | Walterisation Company Ltd | Improvements in the production of phosphate coatings on metal surfaces |
| US3597283A (en) * | 1969-10-08 | 1971-08-03 | Lubrizol Corp | Phosphating solutions for use on ferrous metal and zinc surfaces |
| US3676224A (en) * | 1970-10-16 | 1972-07-11 | Lubrizol Corp | Phosphating solution with scale suppressing characteristics |
| DE2327304C3 (en) * | 1973-05-29 | 1982-01-21 | Metallgesellschaft Ag, 6000 Frankfurt | Process for applying phosphate coatings to metals |
| JPS5165041A (en) * | 1974-12-04 | 1976-06-05 | Nippon Packaging Kk | Kinzokuno rinsanenhimakukeiseihoho |
| US4529451A (en) * | 1983-01-03 | 1985-07-16 | Detrex Chemical Industries, Inc. | Zinc phosphate coated metal and process of producing same |
| DE3311738A1 (en) * | 1983-03-31 | 1984-10-04 | Metallgesellschaft Ag, 6000 Frankfurt | METHOD FOR PHOSPHATING METAL SURFACES |
| EP0172806A4 (en) * | 1984-01-06 | 1986-05-16 | Ford Motor Co | Alkaline resistance phosphate conversion coatings. |
| DE3408577A1 (en) * | 1984-03-09 | 1985-09-12 | Metallgesellschaft Ag, 6000 Frankfurt | METHOD FOR PHOSPHATING METALS |
| US4595424A (en) * | 1985-08-26 | 1986-06-17 | Parker Chemical Company | Method of forming phosphate coating on zinc |
| DE3630246A1 (en) * | 1986-09-05 | 1988-03-10 | Metallgesellschaft Ag | METHOD FOR PRODUCING PHOSPHATE COVER AND ITS APPLICATION |
-
1988
- 1988-07-26 DE DE8888201613T patent/DE3871031D1/en not_active Expired - Lifetime
- 1988-07-26 ES ES198888201613T patent/ES2036666T3/en not_active Expired - Lifetime
- 1988-07-26 EP EP88201613A patent/EP0304108B1/en not_active Expired - Lifetime
- 1988-08-09 CA CA000574254A patent/CA1333147C/en not_active Expired - Fee Related
- 1988-08-12 JP JP63200322A patent/JP2680618B2/en not_active Expired - Lifetime
- 1988-08-19 GB GB8819791A patent/GB2208876B/en not_active Expired - Lifetime
- 1988-08-19 ZA ZA886167A patent/ZA886167B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CA1333147C (en) | 1994-11-22 |
| ES2036666T3 (en) | 1993-06-01 |
| DE3871031D1 (en) | 1992-06-17 |
| GB2208876A (en) | 1989-04-19 |
| ZA886167B (en) | 1990-04-25 |
| JP2680618B2 (en) | 1997-11-19 |
| GB2208876B (en) | 1991-08-14 |
| JPS6468481A (en) | 1989-03-14 |
| EP0304108A1 (en) | 1989-02-22 |
| GB8819791D0 (en) | 1988-09-21 |
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