US3539402A - Solutions for the deposition of protective surface layers on iron and zinc and process therefor - Google Patents
Solutions for the deposition of protective surface layers on iron and zinc and process therefor Download PDFInfo
- Publication number
- US3539402A US3539402A US684491A US3539402DA US3539402A US 3539402 A US3539402 A US 3539402A US 684491 A US684491 A US 684491A US 3539402D A US3539402D A US 3539402DA US 3539402 A US3539402 A US 3539402A
- Authority
- US
- United States
- Prior art keywords
- iron
- solutions
- zinc
- acid
- deposition
- 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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title description 38
- 238000000034 method Methods 0.000 title description 26
- 230000008569 process Effects 0.000 title description 24
- 229910052742 iron Inorganic materials 0.000 title description 19
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title description 14
- 239000011701 zinc Substances 0.000 title description 14
- 229910052725 zinc Inorganic materials 0.000 title description 14
- 230000008021 deposition Effects 0.000 title description 9
- 239000002344 surface layer Substances 0.000 title description 4
- 230000001681 protective effect Effects 0.000 title description 3
- 239000000243 solution Substances 0.000 description 32
- 238000000576 coating method Methods 0.000 description 19
- 229910052751 metal Inorganic materials 0.000 description 19
- 239000002184 metal Substances 0.000 description 19
- 229910000831 Steel Inorganic materials 0.000 description 17
- 239000010959 steel Substances 0.000 description 17
- 239000002253 acid Chemical class 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000002161 passivation Methods 0.000 description 9
- 239000010410 layer Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 150000002739 metals Chemical class 0.000 description 8
- 229910002651 NO3 Inorganic materials 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 7
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 239000007921 spray Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- -1 nitrate ions Chemical class 0.000 description 6
- 239000011241 protective layer Substances 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 239000012141 concentrate Substances 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 150000002222 fluorine compounds Chemical class 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 229910052726 zirconium Inorganic materials 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 235000011007 phosphoric acid Nutrition 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- IDCPFAYURAQKDZ-UHFFFAOYSA-N 1-nitroguanidine Chemical compound NC(=N)N[N+]([O-])=O IDCPFAYURAQKDZ-UHFFFAOYSA-N 0.000 description 2
- YPFNIPKMNMDDDB-UHFFFAOYSA-K 2-[2-[bis(carboxylatomethyl)amino]ethyl-(2-hydroxyethyl)amino]acetate;iron(3+) Chemical compound [Fe+3].OCCN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O YPFNIPKMNMDDDB-UHFFFAOYSA-K 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004922 lacquer Substances 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- RBXVOQPAMPBADW-UHFFFAOYSA-N nitrous acid;phenol Chemical class ON=O.OC1=CC=CC=C1 RBXVOQPAMPBADW-UHFFFAOYSA-N 0.000 description 2
- 150000002913 oxalic acids Chemical class 0.000 description 2
- 239000003973 paint 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
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 2
- 239000011253 protective coating Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- IORISFYTXJVNFE-UHFFFAOYSA-N 2,3-dinitrobenzenesulfonic acid Chemical class OS(=O)(=O)C1=CC=CC([N+]([O-])=O)=C1[N+]([O-])=O IORISFYTXJVNFE-UHFFFAOYSA-N 0.000 description 1
- OVOJUAKDTOOXRF-UHFFFAOYSA-N 2,4-dinitrobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O OVOJUAKDTOOXRF-UHFFFAOYSA-N 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical class [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910015475 FeF 2 Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Chemical class [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 1
- UDSAIICHUKSCKT-UHFFFAOYSA-N bromophenol blue Chemical compound C1=C(Br)C(O)=C(Br)C=C1C1(C=2C=C(Br)C(O)=C(Br)C=2)C2=CC=CC=C2S(=O)(=O)O1 UDSAIICHUKSCKT-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- FZGIHSNZYGFUGM-UHFFFAOYSA-L iron(ii) fluoride Chemical class [F-].[F-].[Fe+2] FZGIHSNZYGFUGM-UHFFFAOYSA-L 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002832 nitroso derivatives Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000006223 plastic coating Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- OCATYIAKPYKMPG-UHFFFAOYSA-M potassium bromate Chemical class [K+].[O-]Br(=O)=O OCATYIAKPYKMPG-UHFFFAOYSA-M 0.000 description 1
- 235000019396 potassium bromate Nutrition 0.000 description 1
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical class [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical class [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
Definitions
- the latter consist of small quantities of complex fluorides of iron, titanium, zirconium or silicon and small amounts of nitrate ions or similar oxidizer in water.
- the pH must carefully be maintained at 1.8 to 3.5.
- the solutions act on the metal surfaces very rapidly, i.e., within 3 to 45 seconds, and are applied at temperatures between 5 and 95 C., preferably at room temperature. Applicataion to the surfaces can be in a bath, by a spray or by roller coating.
- a passivation post-treatment may be applied in the form of aqueous dilute chromic and/ or phosphoric acid or acid salts thereof.
- the invention relates to the deposition of protective coatings on iron, preferably steel, zinc and zinc-clad surfaces, particularly on continuous sheet or coils, by means of acid solutions, whereby the same baths can even simultaneously be used under like conditions for all of these metals. A process for this deposition also is described.
- Another object of the invention is to supply suitable solutions to carry out this process.
- aqueous solution free of chromic, phosphoric and oxalic acids which contains complex fluorides of iron, titanium, zirconium or silicon in amounts of 0.1 to 5 g./l. (grams per liter), calculated on the total cations, and further 0.3 to 10 g./l. nitrate ions or a corresponding amount of other oxidizers.
- the solutions have a pH of 1.8 to 3.5.
- the temperatures are between 5 and C., preferably ambient (room) temperature, i.e., between 10 and 50 C.; and the treatment is carried out within 3 to 45 seconds, and preferably 5 to 30 seconds.
- the values named are the effective amounts, pH, temperatures and times.
- the cations are added to the aqueous bath solutions in the form of their soluble salts whereby, in the case of titanium, zirconium and silicon, their fluoride complexes are most applicable.
- titanyl sulfate or zirconyl chloride can be employed.
- Iron can be added either as complex fluoride or, e.g., as sulfate, nitrate or chloride.
- the baths may contain mixtures of these metals or mixtures of several metal salts,
- the fluoride ions When not entered in the form of complexes, the fluoride ions are incorporated in the baths as hydrofluoric acid or its neutral or acid soluble salts. A slight excess of fluoride ions over the stoichiometrical amount needed for complex formation does not have any adverse effect.
- the bath solutions according to the invention preferably contain soluble nitrates as oxidizer. This permits operation of the baths at particularly low temperatures and short time cycles, thus resulting in very easy procedures.
- the process can be carried out using a solution of iron-III-nitrate and hydrofluoric acid.
- oxidizing agents can be used in lieu of nitrates.
- agents which are known as oxidizing accelerators for phosphatizing solutions, such as sodiumand potassium nitrates, chlorates, bromates, hydrogen peroxide and its adducts, e.g., melamine perhydrate or urea perhydrate (percarbamide), aliphatic and aromatic nitroand nitrosocompounds, e.g., nitroguanidine, picric acid, nitrophenols, monoand dinitrobenzenesulfonic acids. Mixtures of several of these materials may be employed.
- the treating baths are to be practically free from chromic acid and chromium-VI-compounds, of oxalic acid, oxalates, phosphoric acid and phosphates. These compounds or their anions, respectively, inhibit the formation of the layers according to the invention because they themselves are layer-forming anions. Even comparatively small quantities, e.g., of phosphates, decrease the adhesion of organic coatings. Chromic acid and chromium- VI-compounds, moreover, are poisonous, and the effiuents must be decontaminated.
- the pH of the solutions must be adjusted to 1.83.5, and preferably is between 2 and 3. Adjustment can be carried out with alkali solutions or acids other than named in the preceding paragraph. Only when these pH values and the concentrations previously named are maintained, equally good surface layers are produced on iron, steel, zinc and galvanized metal.
- the treatment time is exceedingly short and usually lies between 3 and 45 seconds, preferably to 30 seconds. This time is short enough to carry the conveyors in continuous plants at high speed without the need for particularly large baths or spray zones.
- the temperature of the baths is kept between 5 and 95 C.
- Preferred temperatures are ambient temperatures, i.e., substantially room temperature, between substantially and 50 C. This constitutes a further advantage of the process according to the invention because the baths do not require heating nor necessarily the maintenance of a given temperature.
- the solutions can be applied to the metals by immersion, coating, or spraying. Coating rolls can successfully be employed.
- the metal surfaces are cleaned and degreased prior to the treatment, using the customary organic solvents or alkaline, acid or neutral cleansers.
- the pretreatment is governed by the degree of soiling of the materials.
- a passivation of the layers produced by the process according to the invention is desirable. This can be accomplished by using dilute aqueous phosphoric and/ or chromic acid, or their sodium-, potassiumor ammonium salts, respectively.
- concentrations generally are between 0.01 and 5 g./l.
- the protective layers produced are passivated with aqueous dilute chromic acid which contains chromium-III-ions.
- the effective concentrations generally are 0.2-2 g./l. CrO and 0.05-1 g./l. Cr O
- the layers then are dried after passivation. Prior to the passivation, a water rinse is opportune but not a strict requirement, especially when squeeze rolls are used.
- the baths preferably are renewed with solutions of concentrates, respectively, which contain complex fluorides of iron, titanium, zirconium and/ or silicon and at least one oxidizer and have a ratio of free acid to total acid of 1:1.05 to 1.75.
- the process according to the invention produces uni- .formly thin and readily deformable coatings on iron, steel zinc and galvanized surfaces which impart good corrosion resistance and excellent adhesion of organic coatings subsequently applied.
- the coating layers produced on steel are taupe to bluish-iridescent, those on zinc are gray and, slightly yellowish-iridescent.
- the process is easy to carry out, and the baths have a long working life.
- EXAMPLE 1 A continuous device for coiled or long-strip bands was used, wherein steel and galvanized bands were simultaneously treated by an automatic spray at a dwelling time of 10 seconds in all treatment zones. The surfaces first were degreased with an aqueous alkaline solution of customary composition, and rinsed with cold water, followed by an exposure to an aqueous solution containing Fer, 1.25 NO3 1.5
- Layers thus formed on the steel and zinc surfaces were uniform, thin and well deformable. These layers promoted excellent adhesion of organic coatings, e.g., paints, lacquers and plastic coatings.
- the color of the steel band was taupe to weakly bluish-iridiscent; that of the galvanized bands gray to weakly yellowish-iridescent.
- the spray solution was renewed to maintain it at con stant point using an aqueous concentrate containing Percent Fe(No -9 H O 4 HF (40%) 3 HNO;; (60%) 3
- the protective layer formed did not change from the original even after frequent renewals and much use of the solution.
- EXAMPLE 2 A similar device was used as in Example 1 with a dwelling time of 12 seconds. Iron-, steel and hot dip galvanized (sendzimierverzinkte) iron bands were degreased, rinsed and then simultaneously sprayed with a solution containing G./l. FeF 1.7 N0 3.5
- Iron and steel bands were passivated with 0.1% NaH PO, solution; the galvanized bands with 0.02% chromic acid solution.
- Passivation is an optional step and in many instances is not required.
- Example 1 The spray was the same for all materials which attained thin, uniform and well deformable protective layers. These exhibited excellent adhesion to organic coatings as named in Example 1. When changing over from one band material to another, no changes were required in treatment conditions, i.e., time, pH or temperature.
- a continuous process for the simultaneous deposition of protective surface layers on surfaces of longstn'p bands of like and different metals selected from the group consisting of iron, steel, zinc and zinc-clad iron and steel which consists essentially of continuously passing said bands through a contact zone and continuously contacting said surfaces of said bands with an aqueous solution which is free from phosphoric, chromic and oxalic acids, and which contains complex fluorides of cations selected from the group consisting of iron, and zirconium, in amounts of 0.1 to 5 g./l., calculated on the total cations present, plus 0.1 to 10 g./l.
- oxidizer selected from the group consisting of nitrate ions, sodium and potassium chlorates, sodium and potassium bromates, hydrogen peroxide, melamine perhydrate, urea perhydrate, nitroguanidine, picric acid, nitrophenols and monoand dinitrobenzenesulfonic acid; said aqueous solution having a pH of 1.8 to 3.5 and a temperature of substantially 5 to C.; said bands being continuously contacted with said aqueous solution over a period of time of 3 to 45 seconds; and continuously removing said bands from said contact zone.
- an oxidizer selected from the group consisting of nitrate ions, sodium and potassium chlorates, sodium and potassium bromates, hydrogen peroxide, melamine perhydrate, urea perhydrate, nitroguanidine, picric acid, nitrophenols and monoand dinitrobenzenesulfonic acid
- a passivation step is carried out by a second contacting step to an aqueous solution of a substance selected from the group consisting of phosphoric acid, chromic acid, sodium-, potassiumand ammonium salts of said acids, or mixtures thereof.
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEC0041515 | 1967-02-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3539402A true US3539402A (en) | 1970-11-10 |
Family
ID=7024594
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US684491A Expired - Lifetime US3539402A (en) | 1967-02-16 | 1967-11-20 | Solutions for the deposition of protective surface layers on iron and zinc and process therefor |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US3539402A (en)van) |
| BE (1) | BE710840A (en)van) |
| ES (1) | ES350547A1 (en)van) |
| FR (1) | FR1554415A (en)van) |
| GB (1) | GB1193460A (en)van) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3850732A (en) * | 1970-12-02 | 1974-11-26 | Amchem Prod | Zirconium rinse for phosphate coated metal surfaces |
| US3966502A (en) * | 1972-08-17 | 1976-06-29 | Amchem Products, Inc. | Zirconium rinse for phosphate coated metal surfaces |
| DE3031270A1 (de) * | 1979-09-06 | 1981-03-19 | Richardson Chemical Co., Des Plaines, Ill. | Verfahren zur chromfreien oder chromarmen passivierung von metalloberflaechen und bad zur durchfuehrung des verfahrens |
| US5344504A (en) * | 1993-06-22 | 1994-09-06 | Betz Laboratories, Inc. | Treatment for galvanized metal |
| US20090032144A1 (en) * | 2007-08-03 | 2009-02-05 | Mcmillen Mark W | Pretreatment compositions and methods for coating a metal substrate |
| US20090084682A1 (en) * | 2007-09-28 | 2009-04-02 | Ppg Industries Ohio, Inc. | Methods for coating a metal substrate and related coated metal substrates |
| US20100159258A1 (en) * | 2008-12-18 | 2010-06-24 | Ppg Industries Ohio, Inc. | Methods for passivating a metal substrate and related coated metal substrates |
| US9273399B2 (en) | 2013-03-15 | 2016-03-01 | Ppg Industries Ohio, Inc. | Pretreatment compositions and methods for coating a battery electrode |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2031358C3 (de) * | 1970-06-25 | 1981-10-15 | Gerhard Collardin GmbH, 5000 Köln | Verfahren zur Erzeugung von Schutzschichten auf Aluminium, Eisen und Zink mittels saurer, komplexe Fluoride enthaltender, Lösungen |
| US4496404A (en) * | 1984-05-18 | 1985-01-29 | Parker Chemical Company | Composition and process for treatment of ferrous substrates |
| GB2259920A (en) * | 1991-09-10 | 1993-03-31 | Gibson Chem Ltd | Surface conversion coating solution based on molybdenum and phosphate compounds |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2276353A (en) * | 1935-09-28 | 1942-03-17 | Parker Rust Proof Co | Process of coating |
| US2357219A (en) * | 1942-01-10 | 1944-08-29 | Joseph P Moran | Corrosion-resistant ferrous alloys |
| US3160506A (en) * | 1962-10-19 | 1964-12-08 | Polychrome Corp | Planographic printing plate and method for preparing same |
-
1967
- 1967-11-20 US US684491A patent/US3539402A/en not_active Expired - Lifetime
- 1967-12-06 GB GB55391/67A patent/GB1193460A/en not_active Expired
-
1968
- 1968-02-15 ES ES350547A patent/ES350547A1/es not_active Expired
- 1968-02-16 FR FR1554415D patent/FR1554415A/fr not_active Expired
- 1968-02-16 BE BE710840D patent/BE710840A/xx not_active IP Right Cessation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2276353A (en) * | 1935-09-28 | 1942-03-17 | Parker Rust Proof Co | Process of coating |
| US2357219A (en) * | 1942-01-10 | 1944-08-29 | Joseph P Moran | Corrosion-resistant ferrous alloys |
| US3160506A (en) * | 1962-10-19 | 1964-12-08 | Polychrome Corp | Planographic printing plate and method for preparing same |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3850732A (en) * | 1970-12-02 | 1974-11-26 | Amchem Prod | Zirconium rinse for phosphate coated metal surfaces |
| US3966502A (en) * | 1972-08-17 | 1976-06-29 | Amchem Products, Inc. | Zirconium rinse for phosphate coated metal surfaces |
| DE3031270A1 (de) * | 1979-09-06 | 1981-03-19 | Richardson Chemical Co., Des Plaines, Ill. | Verfahren zur chromfreien oder chromarmen passivierung von metalloberflaechen und bad zur durchfuehrung des verfahrens |
| US5344504A (en) * | 1993-06-22 | 1994-09-06 | Betz Laboratories, Inc. | Treatment for galvanized metal |
| US20090032144A1 (en) * | 2007-08-03 | 2009-02-05 | Mcmillen Mark W | Pretreatment compositions and methods for coating a metal substrate |
| US8673091B2 (en) | 2007-08-03 | 2014-03-18 | Ppg Industries Ohio, Inc | Pretreatment compositions and methods for coating a metal substrate |
| US20090084682A1 (en) * | 2007-09-28 | 2009-04-02 | Ppg Industries Ohio, Inc. | Methods for coating a metal substrate and related coated metal substrates |
| US9574093B2 (en) | 2007-09-28 | 2017-02-21 | Ppg Industries Ohio, Inc. | Methods for coating a metal substrate and related coated metal substrates |
| US20100159258A1 (en) * | 2008-12-18 | 2010-06-24 | Ppg Industries Ohio, Inc. | Methods for passivating a metal substrate and related coated metal substrates |
| US8282801B2 (en) | 2008-12-18 | 2012-10-09 | Ppg Industries Ohio, Inc. | Methods for passivating a metal substrate and related coated metal substrates |
| US9273399B2 (en) | 2013-03-15 | 2016-03-01 | Ppg Industries Ohio, Inc. | Pretreatment compositions and methods for coating a battery electrode |
Also Published As
| Publication number | Publication date |
|---|---|
| BE710840A (en)van) | 1968-08-16 |
| DE1621432B2 (de) | 1975-12-04 |
| ES350547A1 (es) | 1969-05-01 |
| FR1554415A (en)van) | 1969-01-17 |
| DE1621432A1 (de) | 1970-03-26 |
| GB1193460A (en) | 1970-06-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3682713A (en) | Process for applying protective coatings on aluminum,zinc and iron | |
| EP0922785B1 (en) | Treating solution and treating method for forming protective coating films on metals | |
| US2796370A (en) | Composition and method for producing corrosion resistant protective coating on aluminum and aluminum alloys | |
| JP2806531B2 (ja) | 鉄又は鉄合金材料の表面処理用リン酸亜鉛系水溶液及び処理方法 | |
| US3539403A (en) | Solutions for the deposition of protective layers on zinc surfaces and process therefor | |
| US3810792A (en) | Process for the application of phosphate coatings on steel,iron and zinc surfaces | |
| US3539402A (en) | Solutions for the deposition of protective surface layers on iron and zinc and process therefor | |
| US4486241A (en) | Composition and process for treating steel | |
| JPH0365436B2 (en)van) | ||
| CA1333147C (en) | Process of phosphating steel and/or galvanized steel before painting | |
| US3706604A (en) | Process for the coating of metal | |
| JPS6056429B2 (ja) | 金属のリン酸塩皮膜処理方法 | |
| US6027579A (en) | Non-chrome rinse for phosphate coated ferrous metals | |
| US4496404A (en) | Composition and process for treatment of ferrous substrates | |
| JP2845246B2 (ja) | りん酸塩皮膜の形成方法 | |
| US2702768A (en) | Ferrous surface coating process using alkali metal phosphates and hydroxylamines | |
| US2657156A (en) | Phosphate coating composition and process | |
| US3519495A (en) | Process for coating metal surfaces | |
| US3720547A (en) | Permanganate final rinse for metal coatings | |
| US3081238A (en) | Electrolytic treatment of metal surfaces | |
| JP2992619B2 (ja) | 金属上にリン酸塩被膜をつくる方法及びこの方法の使用用途 | |
| US3895969A (en) | Composition and process for inhibiting corrosion of non-ferrous metal surfaced articles and providing surface for synthetic resin coating compositions | |
| US3493440A (en) | Method for phosphate coating ferrous metal surfaces and finishing treatment thereof | |
| US3097978A (en) | Method of coating zinc surfaces | |
| JPS6045705B2 (ja) | 金属表面への燐酸塩被膜の形成方法 |