US3036934A - Coated article and method of making same - Google Patents
Coated article and method of making same Download PDFInfo
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- US3036934A US3036934A US721701A US72170158A US3036934A US 3036934 A US3036934 A US 3036934A US 721701 A US721701 A US 721701A US 72170158 A US72170158 A US 72170158A US 3036934 A US3036934 A US 3036934A
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- United States
- Prior art keywords
- zinc
- film
- metal surface
- acrylic resin
- water
- Prior art date
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- Expired - Lifetime
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- 238000004519 manufacturing process Methods 0.000 title description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 40
- 239000011701 zinc Substances 0.000 claims description 40
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 239000004925 Acrylic resin Substances 0.000 claims description 18
- 229920000178 Acrylic resin Polymers 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 239000000839 emulsion Substances 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 12
- 230000001681 protective effect Effects 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052793 cadmium Inorganic materials 0.000 claims description 6
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 6
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000010408 film Substances 0.000 description 35
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 13
- 239000011347 resin Substances 0.000 description 11
- 229920005989 resin Polymers 0.000 description 11
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 8
- JOSWYUNQBRPBDN-UHFFFAOYSA-P ammonium dichromate Chemical compound [NH4+].[NH4+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O JOSWYUNQBRPBDN-UHFFFAOYSA-P 0.000 description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 6
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 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 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- UYDLBVPAAFVANX-UHFFFAOYSA-N octylphenoxy polyethoxyethanol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(OCCOCCOCCOCCO)C=C1 UYDLBVPAAFVANX-UHFFFAOYSA-N 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- FSVQAZDYQRQQKH-UHFFFAOYSA-N 2-methylbutan-2-yl prop-2-enoate Chemical compound CCC(C)(C)OC(=O)C=C FSVQAZDYQRQQKH-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 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 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- -1 alkyl methacrylates Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- LVGQIQHJMRUCRM-UHFFFAOYSA-L calcium bisulfite Chemical compound [Ca+2].OS([O-])=O.OS([O-])=O LVGQIQHJMRUCRM-UHFFFAOYSA-L 0.000 description 1
- 235000010260 calcium hydrogen sulphite Nutrition 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical class OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 230000009916 joint effect Effects 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/27—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]
- Y10T428/273—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.] of coating
Definitions
- This invention relates to the treatment of zinc and other non-ferrous surfaces, and more particularly to the coating of such surfaces with a composition which will inhibit the formation of white rust Without materially changing the normal appearance of zinc surfaces.
- One object of the invention is to apply a thin, substantially colorless, transparent passivating film on finished zinc surfaces so that the formation of white rust upon such surfaces is inhibited.
- Another object of the invention is to apply a passivating film on zinc surfaces wherein there is substantially no attack of the zinc by the film forming solution.
- a further object of the invention is to produce a passivating film for zinc surfaces which will not hinder subsequent operations, such as forming and painting.
- white rust In the manufacture of zinc-coated steel articles such as sheets or wire, coated by either the hot dip or electrolytic method, frequently a material develops on the zinc surface known as white rust.
- the white rust may appear when the zinc-coated article has been in transit or storage, in a wet or moist atmosphere, for as short a time as a single day. While the exact chemical composition of white rust is open to dispute among various authorities, it is believed to be principally a mixture of zinc hydroxide and zinc carbonate formed by the joint action of moisture and the carbon dioxide, or other corrosive gases, in the air. While the white rust itself does not necessarily promote additional corrosion on the zinc coating, it does mar the commercially pleasing appearance of the zinc surface, and in some cases may interfere with finishing operations.
- Our method comprises immersing the zinc surface in a water emulsion of an acrylic resin to which has been added a controlled amount of a dichromate. A thin film of acrylic resin and dichromate develops on the zinc sulfate. White rust does not appear on a zinc-surfaced article which has been treated by our method, even when the treated article is subsequently subjected to severely humid conditions. Furthermore, when the amount of dichromate in the film does not exceed about 8 mg./sq. ft. no noticeable coloration, or yellow stain, appears in the resultant film.
- Zince-coated articles of any configuration may be treated in which the Zinc surface is readily exposed to the treating solution, the method being particularly adaptable to the treatment of galvanized sheet, strip or wire.
- Our treatment is useful also in the prevention of the white rust effect on cadmium and aluminum.
- any zinc base metal coating such as one formed from high purity zinc (99.9% Zn), technical grade, or high Zinc alloys, is adaptable to the described passivating treatment.
- Example I Sixty parts of a water emulsion containing 46% of an interpolymer of acrylic resin, in this case the product known by the trade name of Rhoplex AC-33, are added to 940 parts of water, to which have been added 4.5 parts of ammonium dichromate. A zinc-coated article is immersed in the thus-prepared aqueous dispersion for a few Example 11 Two hundred and fifty parts of the water emulsion in Example I are added to 750 parts of water, to Which have been added 19 partsof ammonium dichromate.
- a zinccoated article is immersed in the thus prepared aqueous dispersion for a few seconds to wet the surface completely, and is then withdrawn, passed through soft rubber squeegee rolls to remove the excess aqueous dispersion and then air dried, or furnace dried below 325 F. This gives a thin film, approximately 32 mg./sq. ft. in weight.
- the amount of ammonium dichromate in the film be held within the limits of 2 to about 8 mg/sq. ft. of zinc surface. Below 2 mg., only partial protection against white rusting is obtained. Above 8 mg, excessive yellow color develops in the film due to the dichromate. We prefer to have from about 3 to 4.5 mg./sq. ft. of dichromate in the film for best performance against white rusting and for best appearance.
- Comparable results can be obtained by substituting other soluble dichromates or chromates, such as those of sodium and potassium, for the ammonium dichromate.
- the amount of acrylic'resin in the film can be varied over broad limits without impairing the appearance or performance of the film.
- the aqueous dispersion from which the film is formed is very dilute, for example less than 1% to 2% resin solids, in which case the film would have less than 15 mg. of resin per square foot of metal surface, the films are very thin and tend to show a bluish discoloration.
- the film itself may act as a very good paint base for either brush application or baked coatings, while the film appears to have no substantial effect on solde'rabili-ty. Where optimum painting properties are desired, greater amounts of acrylic resin are desirable in the film.
- Example I One foot square sheets of galvanized sheet were coated as in Example I. These were wetted with distilledwater and stacked one upon another, weighted down and permitted to stand for eleven days. Examination after this 3 eleven day period showed that the sheets coated in the manner of Example I were still wet, but were completely free of white rusting. Plain galvanized sheet was 100% covered with white rust. Commercially treated galvanized sheets were also white rusted, in this case to the extent of 5% of the area of the sheet.
- Our film-forming method probably has as its chief application, the treatment of zinc-coated steel strip.
- Our method is quite useful in the treatment of zinc-coated strip made by the hot dip method, for the film may be applied to the strip as the strip leaves the zinc bath without any preliminary treatment of the strip, other than to cool it to room temperature to facilitate the passivating operation.
- the strip In applying our treatment to hot-dip coated strip, the strip, as it leaves the zinc bath, is run through a water bath to cool the strip below about 80 F. As the strip leaves the cooling tank, it is rinsed with clean water and then run directly into the treatment tank a few seconds, or long enough to wet the strip uniformly with treatment solution.
- the strip, with its newly-formed, wet protective film, is Withdrawn from the bath in a vertical direction, and it passes through a pair of rubber squeegee rolls, and then through an air drier.
- the acrylic resin in the form of a Water emulsion, may be a polymer or an interpolymer.
- Water-insoluble polymerized esters of acrylic acid such as methyl acrylate, ethyl acrylate and butyl acrylate, Or their homologs, such as methyl, ethyl and butyl methacrylate, as well as esters of certain higher alcohols, may be used as the resin.
- Mixtures and products of interpolymerization of the foregoing compounds may be used as well.
- acrylic resin in the form of an interpolymer which is useful in our method, can be made by emulsifying, in balanced proportions, in an aqueous medium containing 1 to 12% of a water soluble non-ionic polyethoxyethanol emulsifying agent, the following ingredients:
- a polymerizable, ans-unsaturated monovinylidene carboxylic acid including acrylic, methacrylic and itaconic acids, and water soluble salts thereof,
- At least one polymerizable neutral monomeric monovinylidene ester which by itself forms soft polymers and which is selected from the class consisting of esters of acrylic acid and primary alkanols of 1 to 18 carbon atoms, esters of acrylic acid and secondary alkanols of 1 to 18 carbon atoms, esters of methacrylic acid and pirmary alkanols of 5 to 18 carbon atoms, and esters of methacrylic acid and secondary alkanols of 5 to 18 carbon atoms, and
- At least one polymerizable monovinylidene compound which by itself forms a hard polymer and which is selected from the class consisting of alkyl methacrylates in which the alkyl group has 1 to 4 carbon atoms, tertamyl methacrylate, tert-butyl acrylate, tert-amyl acrylate, cyclohexyl acrylate and cyclohexyl methacrylate, the carboxylate units constituting between 0.5% and 2.5% of the interpolymer, the ratio of parts from said ester to parts from said compound being between 9:1 to 1:20.
- emulsifying agents which may be used are ethylene oxide derivatives of long-chain carboxylic acids.
- one or more inorganic or organic peroxides may be used as well as ammonium, or alkali metal persulfates, or perborates.
- reducing agents sodium hydrosulfite, potassium sulfite and calcium bisulfite.
- the acrylic resin emulsion which we prefer to use is one which results in a dispersion of an interpolymer of ethyl acrylate, methyl methacrylate, and methacrylic acid.
- This resin is made by first preparing a solution of 25 parts of an octylphenoxypolyethoxyethanol, having about 30 ether groups, in 1000 parts of water. A mixture is made of 280 parts of ethyl acrylate, parts of methyl methacrylate, and 5.5 parts of methacrylic acid. This mixture is added, with stirring, to the solution and the resulting mixture cooled to 15 C.
- a solution of 0.5 part of ammonium persulfate in 1.5 parts of water is then added, followed by addition of a solution of 0.6 part of sodium hydrosulfite in six parts of water. Stirring is continued, and the temperature rises to about 65 C. in approximately onehalf hour, after which the mixture is cooled to about 15 C.
- 35 parts of octylphenoxypolyethoxyethanol the same compound as used in preparing the water solution
- 315 parts of ethyl acrylate, parts of methyl methacrylate, 6 parts of methacrylic acid a solution of 0.6 part of ammonium persulfate in 1.5 parts of water, and 0.8 part of sodium hydrosulfite in six parts of water.
- the temperature of the mixture rises, again reaching a maximum of approximately 65 C. Stirring is continued for an hour and the batch cooled to 30 C. While the batch is cooling, ammonium hydroxide solution is added until a pH of 9.5 is reached. The resultant resin is then made into a water emulsion and mixed with the required amount of dichromate or chromate.
- the method of forming a protective film on a metal surface which comprises applying to an article having a metal surface of the group consisting of Zinc, cadmium and aluminum a water mixture consisting essentially of a water emulsion of an acrylic resin and a soluble com- 1 pound of the group consisting of chromates and dichromates and drying and thereby forming a transparent white rust-preventive film of acrylic resin and said soluble compound containing not less than 10 mg. of resin and from 2 mg. to 8 mg. of said soluble compound per square foot of metal surface.
- the method of forming a protective film on a metal surface which comprises applying to an article having a metal surface of the group consisting of zinc, cadmium and aluminum a water mixture consisting essentially of a water emulsion of an acrylic resin in the form of one of the group consisting of polymers, interpolymers and mixtures of polymers and a soluble compound of the group consisting of chromates and dichromates and drying and thereby forming a transparent white rust-preventive film of acrylic resin and said soluble compound, said film containing not less than 10 mg. of resin and from 2 mg. to 8 mg. of said soluble compound per square foot of metal surface.
- the method of forming a protective film on a metal surface which comprises applying to an article having a metal surface of the group consisting of zinc, cadmium and aluminum a water mixture consisting essentially of a water emulsion of an acrylic resin in the form of an interpolymer of an acrylate, methacrylate and a monovinylidene carboxylic acid and ammonium dichromate and drying and thereby forming a transparent white rust-preventive acrylic resin-dichromate film containing not less than 10 mg. of resin and from 2 mg. to 8 mg. of said dichromate per square foot of metal surface.
- the method of forming a protective film on a metal surface which comprises applying to an article having a metal surface of the group consisting of zinc, cadmium and aluminum a water mixture consisting essentially of a Water emulsion of an acrylic resin in the form of an interpolymer of ethyl acrylate, methyl methacrylate and methacrylic acid and ammonium dichromate and drying and thereby forming a transparent white rust-preventive acrylic resin-dichromate film containing not less than 10 mg. of resin and from 2 mg. to 8 mg. of said dichromate per square foot of metal surface.
- a protective film on a metal tive film consisting essentially of not less than surface which comprises applying to an article having a 10 mg. of an acrylic resin and from 2 mg. to 8 mg. of zinc surface a water mixture consisting essentially of a ammonium dichromate per square foot of metal surface.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Description
United States Patent 3,036,934 COATED ARTICLE AND METHOD OF MAKING SAME James B. Horton, Allentown, and Seymour C. Frye,
Coopersburg, Pa., assignors to Bethlehem Steel Company, a corporation of Pennsylvania No Drawing. Filed Mar. 17, 1958, Ser. No. 721,701
6 Claims. (Cl. 117-132) This invention relates to the treatment of zinc and other non-ferrous surfaces, and more particularly to the coating of such surfaces with a composition which will inhibit the formation of white rust Without materially changing the normal appearance of zinc surfaces.
One object of the invention is to apply a thin, substantially colorless, transparent passivating film on finished zinc surfaces so that the formation of white rust upon such surfaces is inhibited.
Another object of the invention is to apply a passivating film on zinc surfaces wherein there is substantially no attack of the zinc by the film forming solution.
A further object of the invention is to produce a passivating film for zinc surfaces which will not hinder subsequent operations, such as forming and painting.
In the manufacture of zinc-coated steel articles such as sheets or wire, coated by either the hot dip or electrolytic method, frequently a material develops on the zinc surface known as white rust. The white rust may appear when the zinc-coated article has been in transit or storage, in a wet or moist atmosphere, for as short a time as a single day. While the exact chemical composition of white rust is open to dispute among various authorities, it is believed to be principally a mixture of zinc hydroxide and zinc carbonate formed by the joint action of moisture and the carbon dioxide, or other corrosive gases, in the air. While the white rust itself does not necessarily promote additional corrosion on the zinc coating, it does mar the commercially pleasing appearance of the zinc surface, and in some cases may interfere with finishing operations.
In the prior treatment of zinc-coated articles, wherein attempts were made to inhibit the formation of white rust thereon, it is known that such articles have been immersed in a chromic acid solution of considerable strength, and then water rinsed. However, the use of strong chromic acid on zinc surfaces produces two serious defects; first, the zinc will in all likelihood be attacked by the chromic acid, and second, a yellow or brownish film appears on the zinc surface. Such treatment is also relatively ineffective in inhibiting white rust.
We have found a treatment for zinc surfaces wherein formation of white rust is effectively inhibited, and the zinc surface remains free of any visible chromic acid or chromate film. Our method comprises immersing the zinc surface in a water emulsion of an acrylic resin to which has been added a controlled amount of a dichromate. A thin film of acrylic resin and dichromate develops on the zinc sulfate. White rust does not appear on a zinc-surfaced article which has been treated by our method, even when the treated article is subsequently subjected to severely humid conditions. Furthermore, when the amount of dichromate in the film does not exceed about 8 mg./sq. ft. no noticeable coloration, or yellow stain, appears in the resultant film.
Our process may be used with equal efficiency on zinc surfaces of the hot-dipped, electroplated or sherardized type. Zince-coated articles of any configuration may be treated in which the Zinc surface is readily exposed to the treating solution, the method being particularly adaptable to the treatment of galvanized sheet, strip or wire. Our treatment is useful also in the prevention of the white rust effect on cadmium and aluminum.
When treating zinc articles, on the surface of which ice foreign matter has been allowed to accumulate after manufacture, it is of course necessary to clean the metal surface prior to introducing the article in the described emulsion. One of the advantages of our invention resides in the fact that the manufactured zinc article can be immersed in the treating solution right after the zinc coating has been applied, as an in-line operation, for in such case no cleaning of the zinc surface is required. Any zinc base metal coating, such as one formed from high purity zinc (99.9% Zn), technical grade, or high Zinc alloys, is adaptable to the described passivating treatment.
The manner by which our invention may be performed is shown by the following illustrative examples:
Example I Sixty parts of a water emulsion containing 46% of an interpolymer of acrylic resin, in this case the product known by the trade name of Rhoplex AC-33, are added to 940 parts of water, to which have been added 4.5 parts of ammonium dichromate. A zinc-coated article is immersed in the thus-prepared aqueous dispersion for a few Example 11 Two hundred and fifty parts of the water emulsion in Example I are added to 750 parts of water, to Which have been added 19 partsof ammonium dichromate. A zinccoated article is immersed in the thus prepared aqueous dispersion for a few seconds to wet the surface completely, and is then withdrawn, passed through soft rubber squeegee rolls to remove the excess aqueous dispersion and then air dried, or furnace dried below 325 F. This gives a thin film, approximately 32 mg./sq. ft. in weight.
It is important that the amount of ammonium dichromate in the film be held within the limits of 2 to about 8 mg/sq. ft. of zinc surface. Below 2 mg., only partial protection against white rusting is obtained. Above 8 mg, excessive yellow color develops in the film due to the dichromate. We prefer to have from about 3 to 4.5 mg./sq. ft. of dichromate in the film for best performance against white rusting and for best appearance.
Comparable results can be obtained by substituting other soluble dichromates or chromates, such as those of sodium and potassium, for the ammonium dichromate.
The amount of acrylic'resin in the film can be varied over broad limits without impairing the appearance or performance of the film. However, if the aqueous dispersion from which the film is formed is very dilute, for example less than 1% to 2% resin solids, in which case the film would have less than 15 mg. of resin per square foot of metal surface, the films are very thin and tend to show a bluish discoloration. We prefer, therefore, to have about 27 mg./sq. ft. of acrylic resin in the film, this being an economic amount which is free of any bluish discoloration. v J The film itself may act as a very good paint base for either brush application or baked coatings, while the film appears to have no substantial effect on solde'rabili-ty. Where optimum painting properties are desired, greater amounts of acrylic resin are desirable in the film.
The high. degree of resistance to white rusting conferred on galvanized sheet, by this invention, may be demonstrated as follows:
One foot square sheets of galvanized sheet were coated as in Example I. These were wetted with distilledwater and stacked one upon another, weighted down and permitted to stand for eleven days. Examination after this 3 eleven day period showed that the sheets coated in the manner of Example I were still wet, but were completely free of white rusting. Plain galvanized sheet was 100% covered with white rust. Commercially treated galvanized sheets were also white rusted, in this case to the extent of 5% of the area of the sheet.
Similarly 48 inch wide sheets, having a length of 48 inches, coated according to Example II, were wetted with distilled water and stacked. No white rust was observed on these sheets after being yet for four weeks. Commercially treated material showed extensive white rusting in this time.
Our film-forming method probably has as its chief application, the treatment of zinc-coated steel strip. Our method is quite useful in the treatment of zinc-coated strip made by the hot dip method, for the film may be applied to the strip as the strip leaves the zinc bath without any preliminary treatment of the strip, other than to cool it to room temperature to facilitate the passivating operation.
In applying our treatment to hot-dip coated strip, the strip, as it leaves the zinc bath, is run through a water bath to cool the strip below about 80 F. As the strip leaves the cooling tank, it is rinsed with clean water and then run directly into the treatment tank a few seconds, or long enough to wet the strip uniformly with treatment solution. The strip, with its newly-formed, wet protective film, is Withdrawn from the bath in a vertical direction, and it passes through a pair of rubber squeegee rolls, and then through an air drier.
The acrylic resin, in the form of a Water emulsion, may be a polymer or an interpolymer. Water-insoluble polymerized esters of acrylic acid, such as methyl acrylate, ethyl acrylate and butyl acrylate, Or their homologs, such as methyl, ethyl and butyl methacrylate, as well as esters of certain higher alcohols, may be used as the resin. Mixtures and products of interpolymerization of the foregoing compounds may be used as well.
One type of acrylic resin in the form of an interpolymer which is useful in our method, can be made by emulsifying, in balanced proportions, in an aqueous medium containing 1 to 12% of a water soluble non-ionic polyethoxyethanol emulsifying agent, the following ingredients:
.(A) A polymerizable, ans-unsaturated monovinylidene carboxylic acid, including acrylic, methacrylic and itaconic acids, and water soluble salts thereof,
(B) At least one polymerizable neutral monomeric monovinylidene ester which by itself forms soft polymers and which is selected from the class consisting of esters of acrylic acid and primary alkanols of 1 to 18 carbon atoms, esters of acrylic acid and secondary alkanols of 1 to 18 carbon atoms, esters of methacrylic acid and pirmary alkanols of 5 to 18 carbon atoms, and esters of methacrylic acid and secondary alkanols of 5 to 18 carbon atoms, and
(C) At least one polymerizable monovinylidene compound, which by itself forms a hard polymer and which is selected from the class consisting of alkyl methacrylates in which the alkyl group has 1 to 4 carbon atoms, tertamyl methacrylate, tert-butyl acrylate, tert-amyl acrylate, cyclohexyl acrylate and cyclohexyl methacrylate, the carboxylate units constituting between 0.5% and 2.5% of the interpolymer, the ratio of parts from said ester to parts from said compound being between 9:1 to 1:20.
Other emulsifying agents which may be used are ethylene oxide derivatives of long-chain carboxylic acids.
As polymerization catalysts, one or more inorganic or organic peroxides may be used as well as ammonium, or alkali metal persulfates, or perborates.
In order to effect interpolymerization at a temperature below that at which coagulation might occur, it is desirable to activate the catalyst. This may be done by using a system in which a reducing agent is present in addition to the catalyst. Examples of reducing agents which may be used are sodium hydrosulfite, potassium sulfite and calcium bisulfite.
The acrylic resin emulsion which we prefer to use is one which results in a dispersion of an interpolymer of ethyl acrylate, methyl methacrylate, and methacrylic acid. This resin is made by first preparing a solution of 25 parts of an octylphenoxypolyethoxyethanol, having about 30 ether groups, in 1000 parts of water. A mixture is made of 280 parts of ethyl acrylate, parts of methyl methacrylate, and 5.5 parts of methacrylic acid. This mixture is added, with stirring, to the solution and the resulting mixture cooled to 15 C. A solution of 0.5 part of ammonium persulfate in 1.5 parts of water is then added, followed by addition of a solution of 0.6 part of sodium hydrosulfite in six parts of water. Stirring is continued, and the temperature rises to about 65 C. in approximately onehalf hour, after which the mixture is cooled to about 15 C. There are now added 35 parts of octylphenoxypolyethoxyethanol (the same compound as used in preparing the water solution), 315 parts of ethyl acrylate, parts of methyl methacrylate, 6 parts of methacrylic acid, a solution of 0.6 part of ammonium persulfate in 1.5 parts of water, and 0.8 part of sodium hydrosulfite in six parts of water. The temperature of the mixture rises, again reaching a maximum of approximately 65 C. Stirring is continued for an hour and the batch cooled to 30 C. While the batch is cooling, ammonium hydroxide solution is added until a pH of 9.5 is reached. The resultant resin is then made into a water emulsion and mixed with the required amount of dichromate or chromate.
We claim:
1. The method of forming a protective film on a metal surface which comprises applying to an article having a metal surface of the group consisting of Zinc, cadmium and aluminum a water mixture consisting essentially of a water emulsion of an acrylic resin and a soluble com- 1 pound of the group consisting of chromates and dichromates and drying and thereby forming a transparent white rust-preventive film of acrylic resin and said soluble compound containing not less than 10 mg. of resin and from 2 mg. to 8 mg. of said soluble compound per square foot of metal surface.
2. The method of forming a protective film on a metal surface which comprises applying to an article having a metal surface of the group consisting of zinc, cadmium and aluminum a water mixture consisting essentially of a water emulsion of an acrylic resin in the form of one of the group consisting of polymers, interpolymers and mixtures of polymers and a soluble compound of the group consisting of chromates and dichromates and drying and thereby forming a transparent white rust-preventive film of acrylic resin and said soluble compound, said film containing not less than 10 mg. of resin and from 2 mg. to 8 mg. of said soluble compound per square foot of metal surface.
3. The method of forming a protective film on a metal surface which comprises applying to an article having a metal surface of the group consisting of zinc, cadmium and aluminum a water mixture consisting essentially of a water emulsion of an acrylic resin in the form of an interpolymer of an acrylate, methacrylate and a monovinylidene carboxylic acid and ammonium dichromate and drying and thereby forming a transparent white rust-preventive acrylic resin-dichromate film containing not less than 10 mg. of resin and from 2 mg. to 8 mg. of said dichromate per square foot of metal surface.
4. The method of forming a protective film on a metal surface which comprises applying to an article having a metal surface of the group consisting of zinc, cadmium and aluminum a water mixture consisting essentially of a Water emulsion of an acrylic resin in the form of an interpolymer of ethyl acrylate, methyl methacrylate and methacrylic acid and ammonium dichromate and drying and thereby forming a transparent white rust-preventive acrylic resin-dichromate film containing not less than 10 mg. of resin and from 2 mg. to 8 mg. of said dichromate per square foot of metal surface.
5. The method of forming a protective film on a metal tive film, said film consisting essentially of not less than surface which comprises applying to an article having a 10 mg. of an acrylic resin and from 2 mg. to 8 mg. of zinc surface a water mixture consisting essentially of a ammonium dichromate per square foot of metal surface. water emulsion of an acrylic resin in the form of an infig if g acrylatei g methacryatg a 5 References Cited in the file of this patent me acry 1c aci an ammonium 1c romate an rying and thereby forming a transparent white rust-preventive UNITED STATES PATENTS acrylic resin-dichromate film containing not less than 10 2,481,323 McCoy Sept. 6, 1949 mg. of resin and from 2 mg. to 8 mg. of said dichromate 2,535,794 Hempel Dec. 26, 1950 per square foot of metal surface. 10 2,760,886 Prentiss et a1. Aug. 28, 1956 6. A zinc-surfaced article having a transparent protec- 2,902,390 Bell Sept. 1, 1959 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No, 3,036 934 May 29 1962 James B. Horton et a1. It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.
Column 1 line 57. for "sulfate" read surface line 66, for "Zince-coated" read Zinc-coated column 2, line 26,, for "32 mg./cq. ft." read 32 mg./sq. ft. c0 1umn 3 line 10, for "yet" read wet line 51 for "plrmary" read primary Signed and sealed this 4th day of September 1962.
(SEAL) Attest:
ERNEST w. SWIDER DAVID LADD Commissioner of Patents Attesting Officer
Claims (1)
1. THE METHOD OF FORMING A PROTECTIVE FILM ON A METAL SURFACE WHICH COMPRISES APPLYING TO AN ARTICLE HAVING A METAL SURFACE OF THE GROUP CONSISTING OF ZINC, CADMIUM AND ALUMINUM A WATER MIXTURE CONSISTING ESSENTIALLY OF A WATER EMULSION OF AN ACRYLIC RESIN AND A SOLUBLE COMPOUND OF THE GROUP CONSISTING OF CHROMATES AND DICHROMATES AND DRYING AND THEREBY FORMING A TRANSPARENT WHITE RUST-PREVENTIVE FILM OF ACRYLIC RESIN AND SAID SOLUBLE COMPOUND CONTAINING NOT LESS THAN 10 MG. OF RESIN AND FROM 2 MG. TO 8 MG. OF SAID SOLUBLE COMPOUND PER SQUARE FOOT OF METAL SURFACE.
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US721701A US3036934A (en) | 1958-03-17 | 1958-03-17 | Coated article and method of making same |
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Cited By (14)
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US3094435A (en) * | 1961-02-09 | 1963-06-18 | Pennsalt Chemicals Corp | Coating with thermosetting resin |
US3185596A (en) * | 1960-10-10 | 1965-05-25 | Amchem Prod | Method of coating metal |
US3298848A (en) * | 1965-10-04 | 1967-01-17 | Fritz H W Wachholtz | Aqueous dispersion of modified drying and semi-drying oils containing watersoluble drier |
US3328492A (en) * | 1963-04-22 | 1967-06-27 | Hexionic Acid Corp | Sorbitol and mannitol esters of phosphoric acid and salts thereof |
US3413158A (en) * | 1964-02-13 | 1968-11-26 | Yawata Iron & Steel Co | Water-dispersed coating compositions |
US3437574A (en) * | 1964-08-31 | 1969-04-08 | Kansai Paint Co Ltd | Anticorrosive treatment of zinc and metallic materials coated with zinc |
US3485781A (en) * | 1968-01-05 | 1969-12-23 | Ashland Oil Inc | Cross-linking of water soluble or water-dispersible polyesters with dichromates |
US3505128A (en) * | 1964-10-07 | 1970-04-07 | Yawata Seitetsu Kk | Aqueous metal-coating composition |
US3607452A (en) * | 1968-06-19 | 1971-09-21 | Michael N Marosi | Color coating for aluminum products |
US3791431A (en) * | 1966-06-01 | 1974-02-12 | Amchem Prod | Process for coating metals |
US3901836A (en) * | 1973-10-04 | 1975-08-26 | Chem Paint Specialties Inc | Rust preventative coating for metallic surfaces consisting of water-soluble resin and sodium benzoate-potassium tripolyphosphate rust inhibitor |
US4373968A (en) * | 1981-06-24 | 1983-02-15 | Amchem Products, Inc. | Coating composition |
US4781988A (en) * | 1986-09-29 | 1988-11-01 | Owens-Corning Fiberglas Corporation | Corrosion-resistant coating |
US20070107164A1 (en) * | 2003-05-10 | 2007-05-17 | Edscha Ag | Assembly aid and method for positioning a hinge in a reproducible manner |
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US2535794A (en) * | 1947-01-24 | 1950-12-26 | Heresite & Chemical Company | Method of preparing ferrous metal objects for the application of synthetic resins |
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US2535794A (en) * | 1947-01-24 | 1950-12-26 | Heresite & Chemical Company | Method of preparing ferrous metal objects for the application of synthetic resins |
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Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3185596A (en) * | 1960-10-10 | 1965-05-25 | Amchem Prod | Method of coating metal |
US3094435A (en) * | 1961-02-09 | 1963-06-18 | Pennsalt Chemicals Corp | Coating with thermosetting resin |
US3328492A (en) * | 1963-04-22 | 1967-06-27 | Hexionic Acid Corp | Sorbitol and mannitol esters of phosphoric acid and salts thereof |
US3413158A (en) * | 1964-02-13 | 1968-11-26 | Yawata Iron & Steel Co | Water-dispersed coating compositions |
US3437574A (en) * | 1964-08-31 | 1969-04-08 | Kansai Paint Co Ltd | Anticorrosive treatment of zinc and metallic materials coated with zinc |
US3505128A (en) * | 1964-10-07 | 1970-04-07 | Yawata Seitetsu Kk | Aqueous metal-coating composition |
US3298848A (en) * | 1965-10-04 | 1967-01-17 | Fritz H W Wachholtz | Aqueous dispersion of modified drying and semi-drying oils containing watersoluble drier |
US3791431A (en) * | 1966-06-01 | 1974-02-12 | Amchem Prod | Process for coating metals |
US3485781A (en) * | 1968-01-05 | 1969-12-23 | Ashland Oil Inc | Cross-linking of water soluble or water-dispersible polyesters with dichromates |
US3607452A (en) * | 1968-06-19 | 1971-09-21 | Michael N Marosi | Color coating for aluminum products |
US3901836A (en) * | 1973-10-04 | 1975-08-26 | Chem Paint Specialties Inc | Rust preventative coating for metallic surfaces consisting of water-soluble resin and sodium benzoate-potassium tripolyphosphate rust inhibitor |
US4373968A (en) * | 1981-06-24 | 1983-02-15 | Amchem Products, Inc. | Coating composition |
US4781988A (en) * | 1986-09-29 | 1988-11-01 | Owens-Corning Fiberglas Corporation | Corrosion-resistant coating |
US20070107164A1 (en) * | 2003-05-10 | 2007-05-17 | Edscha Ag | Assembly aid and method for positioning a hinge in a reproducible manner |
US8220125B2 (en) * | 2003-05-10 | 2012-07-17 | Edscha Ag | Assembly aid and method for positioning a hinge in a reproducible manner |
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