US2276353A - Process of coating - Google Patents
Process of coating Download PDFInfo
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- US2276353A US2276353A US42670A US4267035A US2276353A US 2276353 A US2276353 A US 2276353A US 42670 A US42670 A US 42670A US 4267035 A US4267035 A US 4267035A US 2276353 A US2276353 A US 2276353A
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- 238000000576 coating method Methods 0.000 title description 52
- 239000011248 coating agent Substances 0.000 title description 49
- 238000000034 method Methods 0.000 title description 10
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 36
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 18
- 229910052751 metal Inorganic materials 0.000 description 18
- 239000002184 metal Substances 0.000 description 18
- 239000004317 sodium nitrate Substances 0.000 description 18
- 235000010344 sodium nitrate Nutrition 0.000 description 18
- 229910000831 Steel Inorganic materials 0.000 description 17
- 239000010959 steel Substances 0.000 description 17
- 229910052782 aluminium Inorganic materials 0.000 description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 16
- 239000004615 ingredient Substances 0.000 description 16
- 239000002253 acid Substances 0.000 description 10
- 229910052742 iron Inorganic materials 0.000 description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 8
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 8
- 210000003298 dental enamel Anatomy 0.000 description 8
- 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 8
- 239000004922 lacquer Substances 0.000 description 8
- 239000007800 oxidant agent Substances 0.000 description 8
- 239000003973 paint Substances 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- 229910052725 zinc Inorganic materials 0.000 description 8
- 230000001464 adherent effect Effects 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229960002163 hydrogen peroxide Drugs 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 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
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 241001124532 Bubalus depressicornis Species 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical class [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 1
- 241001579016 Nanoa Species 0.000 description 1
- 241000549556 Nanos Species 0.000 description 1
- 235000010676 Ocimum basilicum Nutrition 0.000 description 1
- 240000007926 Ocimum gratissimum Species 0.000 description 1
- 229910004072 SiFe Inorganic materials 0.000 description 1
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- NAAXGLXYRDSIRS-UHFFFAOYSA-L dihydrogen phosphate;manganese(2+) Chemical compound [Mn+2].OP(O)([O-])=O.OP(O)([O-])=O NAAXGLXYRDSIRS-UHFFFAOYSA-L 0.000 description 1
- -1 enamels Substances 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- PXLIDIMHPNPGMH-UHFFFAOYSA-N sodium chromate Chemical compound [Na+].[Na+].[O-][Cr]([O-])(=O)=O PXLIDIMHPNPGMH-UHFFFAOYSA-N 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/10—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by other chemical means
-
- 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
-
- 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
- C23C22/37—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 hexavalent chromium compounds
Definitions
- Patented Mar. 17, 1942 PROCESS F COATING .lolm S. Thompson, Detroit, Mich, assignor to harass Rust Proof (Jemuany, Detroit, Mich.
- This invention relates to the field of the chemical coating of metals.
- An object of the invention is the rendering of metallic surfaces resistant to corrosion.
- a further object of the inven-- tion is to form on metallic surfaces a chemical coating which resists corrosion when coated with a paint, lacquer, or enamel and provides a base coat to which the applied coatings adhere in a much firmer manner than they would to the bare metal.
- the invention comprises the use of solutions containing soluble hydrofluosilicic compounds with the addition of an oxidizing agent with or without accelerating agents.
- Hydrofiuosillcic acid (HaSiFa) and soluble salts of this acid are comprised generally.
- oxidizing agents such as hydrogen peroxide may be employed and accelerating agents such as nitrates may be used.
- the process comprises generally treatment of the metal surface by any of the ordinary methods.
- the metallic surfaces were immersed in the solutions at a boiling ⁇ .temperature.
- the usual processing time was 5 minutes, although this may be decreased if desired.
- the essential thing is to bring about a reaction between the surface of the metal and the solution and that the time, temperature, and other factors of operation may be varied considerably without departing from the scope of the invention.
- 2" x 4" panels were employed in the usual case.
- Example 1 A sheet of aluminum was immersed in a 200 cc. solution to which had been added /2 gram chromic acid, 3 cc. HaSiFc. The metal was removed after 5 minutes at a boiling temperature and a hard, medium gray, very uni- ?form coating had been produced upon the surface "of the aluminum. When the same ingredients are used with the addition of 2 grams of sodium nit'rate, a brown coating is obtained which is liner .and softer.
- Example 2 The same conditions as in Example 1 were employed using a solution containing gram chromic acid and 5 grains manganese silicofluoride. A medium gray. very uniform, medium hard coating was obtained on the alumimm. when 2 grams of sodium nitrate is used with the other ingredients a harder, lighter, thinner coating is obtained.
- Example 3 Under the same conditions as in Example 1 a solution was employed containing V3 gram chromic acid, and 5 grams sodium silicofluoride. Th aluminum surface had a hard thin, light gray coating. When 2 grams of sodium nitrate is used with the other ingredients the same result is obtained.
- Example 4 Under the same conditions as in Example 1 an aluminum sheet was treated with a solution containing 2 cc. of hydrogen peroxide and 3 cc. hydrofiuosilicic acid. Coatings were obtained which may be described as white, under a fairly hard gray surface. When 2 grams of sodium nitrate is employed with the other ingredients a medium gray, fairly hard coating is obtained.
- Example 5 Under the same conditions as in mample 1 an aluminum object is immersed in a solution to which has been added 1 gram potasslum permanganate and 3 cc. hydrofluosilicic acid.
- a red-purple iridescent fairly hard coating is obtained. When 2 grams of sodium nitrate is used with the same ingredients 8 dark purple, soft and dusty coating is obtained.
- Example 6 Under the same conditions as in the preceding examples a solution was employed using 2 grams potassium dichromate and 5 cc. hy-
- Example 7 Under the same conditions as in the preceding examples a solution is used containing 2 grams sodium chromate with 3 cc. hydrofluosiiicic acid. A dark gray, hard coating is obtained on the aluminum surface. When 2 grams of sodium nitrate is used together with the other ingredients a light brown, hard, thin coating is obtained.
- Example 8 Under the same conditions an aluminum surface is treated with a solution containing 2'grams chromium sulphat and 3 cc. hy-' drofluosilicic acid. There is obtained on the aluminum surface a soft green gray coating over a hard thin white. When 2 grams sodium nitrate is used together with the other ingredients, a thin,"
- Example lib-The solution employed was made up by adding 1 gram chromic acid, 2% cc. Basil;
- Example 11 Under the same conditions as in the preceding examples a steel object was processed in a solution containing 2 grams chromlc acid, 5 grams manganese silicofluoride, 2% grams sodium nitrate for 1 to 5 minutes. There was obtained a black, adherent coating. The same results were obtained with the following ingredients in solution:
- Example 16 Under the same conditions as in the preceding examples a steel object was processed in a solution containing 2 co.HaSiFs+l cc.
- Example 17 Under the same conditions as in the preceding examples a steel object was processed in a solution containing 2 cc. HaSiFs and suited in 5 minutes which was adherent under a loose top dust.
- Example 18 Underthe same conditions as in the preceding examples a steel object was processed in a solution containing 1 cc. HaSiFs+2 gr. KaSzOa. A thin-iridescent coating resulted in 5 minutes but the addition of 2 grams NaNOl to this solution produced a dark gray coating.
- Example 19 Under the same conditions as the preceding examples a steel object was processed in a solution containing 6 gr. NaIhPO4+6 gr. MnSiFs+4 gr. Mn(NO:)z and a gray adherent coating resulted in 15 minutes at boiling temperature.
- Manganese dihydrogen phosphate may be substituted for the sodium phosphate in this example and FeSiFs or ZllSiFs may be substituted for the MnSiF'o.
- Example 20 Under the same conditions as in the preceding examples a steel object was processed in a solution containing 2 /2 cc. HzSiFs and 2 gr. NaNOs. A very uniform soft gray coating resulted in 5 minutes. 5 gr. MllSiFs may be substituted for the H1811"; in this combination and very good corrosion resistance is shown from both treatments.
- Example 21.-A 200 cc. solution containing 5 gr. MnSiFa+.2 cc. 85% 8.1904 produced a good coating in 5 minutes.
- the addition of 2 grams NaNOl to this solution also produced a resistant 1 gr. KMnOa A gray and brown coating recoating in 5 minutes.
- FeSiFs may be substituted for MnSiFs and Mn(NOa)z may be substituted for the NaNOa.
- Example 22 -1 gram CrO: plus 2 cc. HzSiFs.
- a thin gray, fairly hard coating was obtained.
- sodium nitrate is used with the other ingredients a coating is obtained which is gray with green tint, fairly hard and uniform.
- manganese nitrate or zinc nitrate similar results are obtained.
- aluminum nitrate is employed in place of the sodium nitrate a coating is obtained which is hard, adherent and heavy gray.
- Example 23 -2 grams chromium sulphate plus 2 cc. HzSiFs. When 2 grams of sodium nitrate is used with the other ingredients a uniform, dark, dull, hard, adherent coating was obtained.
- Example 25.1 gram CrO plus 5 grams MnSiFs, A coating is obtained similar to that when using HaSiFs in place of MIlSiFs. When 2 grams sodium nitrate is employed with the other ingredients a green coating is obtained.
- metals other than those specifically mentioned can be processed.
- Time, temperatures, proportions and ingredients can be varied well within the scope of the invention, the essence being the treatment of metals with solutions containing the SiFc radical together with the use of oxidizing agents with or without accelerating agents.
- the examples mentioned above include hydrogen-peroxide, nitric acid and nitrates, chromic acid, chromates and dichromates, permanganates, sulphurous acid and sulphites, chloric and perchloric acids and chlorates, molybdates, tungstates, and persulphates, which are recognized oxidizing agents, and other compatible oxidizing agents may be used.
- the oxidizing agent must, of course, be a compatible material, that is, it must be soluble in the solution and its oxidizing power must not be destroyed by the other ingredients in the solution before it has an opportunity to exert its oxidizing power in the chemical reaction that takes place at the surface of the work.
- a process of treating a surface of a metal included in the group consisting of iron, steel, zinc, aluminum and their alloys which comprises subjecting said surfaces to the action of a heated solution containing the SiFe radical and one of the group consisting of chromic acid and nitric acid, and treating the metallic surface until a visible protective paint-holding coating is obtained thereon and then applying a coating of one of the group consisting of paints, lacquers and enamels.
- a process'of treating a surface of a metal included in the group consisting of iron, steel, zinc,'aluminum and their alloys which comprises subjecting said surfaces to the action of a heated solution containing a soluble hexavalent chromium compound and one of the group of HzSiFs and soluble salts thereof, at least one of the aforesaid being added in the form of acid and continuing such action until a visible protective paint-holding coating is obtained upon the metallie surface and thereafter applying a coating of one of the group consisting of paints, lacquers and enamels.
- a process of treating a surface of a metal included in the group consisting of iron, steel, zinc, aluminum and their alloys which comprises subjecting said surfaces to the action 'of a heated solution containing chromic acid and one of the group of HzSiFa and soluble salts thereof, and continuing such action until a visible protective paint-holding coating is obtained upon the metallic surface and thereafter applying a coating of one of the group consisting of paints, lacquers and enamels.
- a process which comprises treating a surface of a metal included in the group consisting of iron, steel, zinc, aluminum and their alloys with a heated solution containing the radical SiFc and nitric acid, and continuing such treatment until a visible, protective paint-holding coating is obtained upon the metallic surface and thereafter coating the surface with one of the group consisting of paints, lacquers and enamels.
- a process of treating a surface of a metal included in the group consisting of iron, steel, zinc, aluminum and their alloys which comprises subjecting said surfaces to the action of an acidulated heated solution containing as its chief active ingredients the SiFs radical and a compatible oxidizing agent of the group consisting paints, lacquers and enamels.
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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
Patented Mar. 17, 1942 PROCESS F COATING .lolm S. Thompson, Detroit, Mich, assignor to harass Rust Proof (Jemuany, Detroit, Mich.
No Drawing. Application September 28, 1935, Serial No. 42,670. Renewed August 28, 1938 This invention relates to the field of the chemical coating of metals. An object of the invention is the rendering of metallic surfaces resistant to corrosion. A further object of the inven-- tion is to form on metallic surfaces a chemical coating which resists corrosion when coated with a paint, lacquer, or enamel and provides a base coat to which the applied coatings adhere in a much firmer manner than they would to the bare metal.
Generally speaking, the invention comprises the use of solutions containing soluble hydrofluosilicic compounds with the addition of an oxidizing agent with or without accelerating agents. Hydrofiuosillcic acid (HaSiFa) and soluble salts of this acid are comprised generally. oxidizing agents such as hydrogen peroxide may be employed and accelerating agents such as nitrates may be used.
By the use of these materials surfaces of metals such as iron, steel, aluminum and zinc and alloys are rendered rust resistant and in many cases coatings are formed which serve as a rust resisting base for paints, lacquers, enamels, and other coating compositions.
The process comprises generally treatment of the metal surface by any of the ordinary methods. .In the following examples which are given by way of illustration and not limitation the metallic surfaces were immersed in the solutions at a boiling }.temperature. The usual processing time was 5 minutes, although this may be decreased if desired. 'It is understood that the essential thing is to bring about a reaction between the surface of the metal and the solution and that the time, temperature, and other factors of operation may be varied considerably without departing from the scope of the invention. In the following examples 2" x 4" panels were employed in the usual case.
Example 1.--A sheet of aluminum was immersed in a 200 cc. solution to which had been added /2 gram chromic acid, 3 cc. HaSiFc. The metal was removed after 5 minutes at a boiling temperature and a hard, medium gray, very uni- ?form coating had been produced upon the surface "of the aluminum. When the same ingredients are used with the addition of 2 grams of sodium nit'rate, a brown coating is obtained which is liner .and softer.
Example 2.-The same conditions as in Example 1 were employed using a solution containing gram chromic acid and 5 grains manganese silicofluoride. A medium gray. very uniform, medium hard coating was obtained on the alumimm. when 2 grams of sodium nitrate is used with the other ingredients a harder, lighter, thinner coating is obtained.
Example 3.--Under the same conditions as in Example 1 a solution was employed containing V3 gram chromic acid, and 5 grams sodium silicofluoride. Th aluminum surface had a hard thin, light gray coating. When 2 grams of sodium nitrate is used with the other ingredients the same result is obtained.
Example 4.Under the same conditions as in Example 1 an aluminum sheet was treated with a solution containing 2 cc. of hydrogen peroxide and 3 cc. hydrofiuosilicic acid. Coatings were obtained which may be described as white, under a fairly hard gray surface. When 2 grams of sodium nitrate is employed with the other ingredients a medium gray, fairly hard coating is obtained.
Example 5.--Under the same conditions as in mample 1 an aluminum object is immersed in a solution to which has been added 1 gram potasslum permanganate and 3 cc. hydrofluosilicic acid.
A red-purple iridescent fairly hard coating is obtained. When 2 grams of sodium nitrate is used with the same ingredients 8 dark purple, soft and dusty coating is obtained.
Example 6.-Under the same conditions as in the preceding examples a solution was employed using 2 grams potassium dichromate and 5 cc. hy-
drofluosilicic acid. A rather soft gray coating is obtained on the aluminum. When 2 grams of sodium nitrate is used with the other ingredients 9. hard, brown coating is obtained.
Example 7.-Under the same conditions as in the preceding examples a solution is used containing 2 grams sodium chromate with 3 cc. hydrofluosiiicic acid. A dark gray, hard coating is obtained on the aluminum surface. When 2 grams of sodium nitrate is used together with the other ingredients a light brown, hard, thin coating is obtained.
Example 8.-Under the same conditions an aluminum surface is treated with a solution containing 2'grams chromium sulphat and 3 cc. hy-' drofluosilicic acid. There is obtained on the aluminum surface a soft green gray coating over a hard thin white. When 2 grams sodium nitrate is used together with the other ingredients, a thin,"
2 was taken. There was obtained on a steel surface a dark, gray, fairly hard coating.
Example lib-The solution employed was made up by adding 1 gram chromic acid, 2% cc. Basil;
and 2 grams sodium nitrate. A black, adherent coating .was obtained under a brown dust on a steel surface in 5 minutes.
Example 11.Under the same conditions as in the preceding examples a steel object was processed in a solution containing 2 grams chromlc acid, 5 grams manganese silicofluoride, 2% grams sodium nitrate for 1 to 5 minutes. There was obtained a black, adherent coating. The same results were obtained with the following ingredients in solution:
2 grams CrOa plus 5 gramsFeSiFa plus 2% grams N'aNOa 2 gr. Cr05+5 gr. FeSiFe+2 gr. MniNOa):
2 gr. Cra+3 cc. Fea(SiFs)s+2 gr. NaNO:
10 cc. H2SiFc+4 gr. KzCr0+2 gr. mason:
cc. HaSiFe+2 gr. KaCnO1+2 gr. ammo:
2 gr. Cr:(SO4)a+5 cc. HaSiFs+2 gr. NaNOl Example 12.--Under the same conditions as in the preceding examples a steel object was proc-' essed in a solution containing 1 cc. HsSiFs+3 gr. K1804 for 5 minutes. vA like solution with 2 gr. NaNO: added gave the same rust proofing results as tested in the salt spray, both being an improvement over non-treated. steel.
Example 13.-Other salts that may be substituted for K2804 in the combinations given in the example Just above are:
NaCl NaaSOs NaHzPOs NaHaPOs NMMOOQ KClO: NMWOs N82340:
HCl HNO:
HsPO4 H280:
HsPOa H010:
HClQ4 Boric acid Molybdio acid Tungstic acid Slight variations in proportions may be necessary in the chemicals used in these examples, but added corrosion resistance is. obtained from all of them.
Example 16.-Under the same conditions as in the preceding examples a steel object was processed in a solution containing 2 co.HaSiFs+l cc.
30% H202. A soft brown and black coating re sulted in 5 minutes. Alike solution containing 1 cc. HzSiFs+1 cc. 30% H202+2 gr. NaNO: produced a very uniform, adherent, light gray coating in 5 minutes. Both of these treatments gave exceptionally good salt spray test results.
Example 17.Under the same conditions as in the preceding examples a steel object was processed in a solution containing 2 cc. HaSiFs and suited in 5 minutes which was adherent under a loose top dust.
Example 18.Underthe same conditions as in the preceding examples a steel object was processed in a solution containing 1 cc. HaSiFs+2 gr. KaSzOa. A thin-iridescent coating resulted in 5 minutes but the addition of 2 grams NaNOl to this solution produced a dark gray coating.
Example 19.Under the same conditions as the preceding examples a steel object was processed in a solution containing 6 gr. NaIhPO4+6 gr. MnSiFs+4 gr. Mn(NO:)z and a gray adherent coating resulted in 15 minutes at boiling temperature. Manganese dihydrogen phosphate may be substituted for the sodium phosphate in this example and FeSiFs or ZllSiFs may be substituted for the MnSiF'o.
Example 20..Under the same conditions as in the preceding examples a steel object was processed in a solution containing 2 /2 cc. HzSiFs and 2 gr. NaNOs. A very uniform soft gray coating resulted in 5 minutes. 5 gr. MllSiFs may be substituted for the H1811"; in this combination and very good corrosion resistance is shown from both treatments.
Example 21.-A 200 cc. solution containing 5 gr. MnSiFa+.2 cc. 85% 8.1904 produced a good coating in 5 minutes. The addition of 2 grams NaNOl to this solution also produced a resistant 1 gr. KMnOa A gray and brown coating recoating in 5 minutes. In this example FeSiFs may be substituted for MnSiFs and Mn(NOa)z may be substituted for the NaNOa.
In thefollowing examples objects with a zinc surface were immersed in a boiling solution for 5 minutes.
Example 22.-1 gram CrO: plus 2 cc. HzSiFs.
A thin gray, fairly hard coating was obtained. When 2 grams of sodium nitrate is used with the other ingredients a coating is obtained which is gray with green tint, fairly hard and uniform. In this example if sodium nitrate is replaced by manganese nitrate or zinc nitrate similar results are obtained. When aluminum nitrate is employed in place of the sodium nitrate a coating is obtained which is hard, adherent and heavy gray.
Example 23.-2 grams chromium sulphate plus 2 cc. HzSiFs. When 2 grams of sodium nitrate is used with the other ingredients a uniform, dark, dull, hard, adherent coating was obtained.
Example 24.1 gram CrO: plus 1 gram KMnOr plus 2 cc. HaSiFa. A hard gray coating under a soft purple one is obtained. When 2 grams of sodium nitrate is used with the other ingredients similar results are obtained.
Example 25.1 gram CrO: plus 5 grams MnSiFs, A coating is obtained similar to that when using HaSiFs in place of MIlSiFs. When 2 grams sodium nitrate is employed with the other ingredients a green coating is obtained.
Example 26.--2 cc. HaSiFs plus 2 grams sodium nitrate. A transparent, fairly hard, dark gray coating is obtained. When zinc nitrate is .used in place of sodium nitrate, similar results are obtained. Example 27.--1 gram chromic acid plus 1 gram of K2820: plus 1 cc. mSiFa. A hard gray mixed dark and light coating is obtained. When 2 grams sodium nitrate are'used with the other ingredients a soft, dark green shiny finish is obtained. 1
In the above examples metals other than those specifically mentioned can be processed. Time, temperatures, proportions and ingredients can be varied well within the scope of the invention, the essence being the treatment of metals with solutions containing the SiFc radical together with the use of oxidizing agents with or without accelerating agents.
The examples mentioned above include hydrogen-peroxide, nitric acid and nitrates, chromic acid, chromates and dichromates, permanganates, sulphurous acid and sulphites, chloric and perchloric acids and chlorates, molybdates, tungstates, and persulphates, which are recognized oxidizing agents, and other compatible oxidizing agents may be used. The oxidizing agent must, of course, be a compatible material, that is, it must be soluble in the solution and its oxidizing power must not be destroyed by the other ingredients in the solution before it has an opportunity to exert its oxidizing power in the chemical reaction that takes place at the surface of the work.
It has been found that acceleration is gained by adding to these solutions a soluble salt of a metal below the respective metal being treated in the electromotive series. This acceleration is apparent in quickening of processing time, more uniformity in the coating and in producing aheavier coating. In the case of treating an iron surface, salts of metals slightly above iron in the electromotive series may be used.
What I claim is:
1. A process of treating a surface of a metal included in the group consisting of iron, steel, zinc, aluminum and their alloys, which comprises subjecting said surfaces to the action of a heated solution containing the SiFe radical and one of the group consisting of chromic acid and nitric acid, and treating the metallic surface until a visible protective paint-holding coating is obtained thereon and then applying a coating of one of the group consisting of paints, lacquers and enamels.
2. A process'of treating a surface of a metal included in the group consisting of iron, steel, zinc,'aluminum and their alloys, which comprises subjecting said surfaces to the action of a heated solution containing a soluble hexavalent chromium compound and one of the group of HzSiFs and soluble salts thereof, at least one of the aforesaid being added in the form of acid and continuing such action until a visible protective paint-holding coating is obtained upon the metallie surface and thereafter applying a coating of one of the group consisting of paints, lacquers and enamels.
3. A process of treating a surface of a metal included in the group consisting of iron, steel, zinc, aluminum and their alloys, which comprises subjecting said surfaces to the action 'of a heated solution containing chromic acid and one of the group of HzSiFa and soluble salts thereof, and continuing such action until a visible protective paint-holding coating is obtained upon the metallic surface and thereafter applying a coating of one of the group consisting of paints, lacquers and enamels.
4. A process which comprises treating a surface of a metal included in the group consisting of iron, steel, zinc, aluminum and their alloys with a heated solution containing the radical SiFc and nitric acid, and continuing such treatment until a visible, protective paint-holding coating is obtained upon the metallic surface and thereafter coating the surface with one of the group consisting of paints, lacquers and enamels.
5- A process of treating a surface of.a metal included in the group consisting of iron, steel,
zinc, aluminum and their alloys, which comprises subjecting said surfaces to the action of an aciduated heated solution containing as its chief active ingredients the SiFs radical and a compatible oxidizing agent, and treating the metallic surface until a visible protective paint-holding coating is obtained and thereafter applying to the metal surfacea coating of one of the group consisting of paints, lacquers and enamels.
6. A process of treating a surface of a metal included in the group consisting of iron, steel, zinc, aluminum and their alloys, which comprises subjecting said surfaces to the action of an acidulated heated solution containing as its chief active ingredients the SiFs radical and a compatible oxidizing agent of the group consisting paints, lacquers and enamels.
JOHN S. THOMPSON.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US42670A US2276353A (en) | 1935-09-28 | 1935-09-28 | Process of coating |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US42670A US2276353A (en) | 1935-09-28 | 1935-09-28 | Process of coating |
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| US2276353A true US2276353A (en) | 1942-03-17 |
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| US42670A Expired - Lifetime US2276353A (en) | 1935-09-28 | 1935-09-28 | Process of coating |
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Cited By (48)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2434237A (en) * | 1943-09-13 | 1948-01-06 | Sk Wellman Co | Apparatus for applying powdered metal briquets to curved metallic surfaces |
| US2434525A (en) * | 1943-08-23 | 1948-01-13 | Rheem Mfg Co | Coating on metals |
| US2454799A (en) * | 1944-12-09 | 1948-11-30 | Hart David | Method of producing protective coatings on magnesium powder |
| US2497905A (en) * | 1945-03-03 | 1950-02-21 | Rheem Mfg Co | Coating zinc or cadmium to impart corrosion and abrasion resistance |
| US2500672A (en) * | 1949-06-08 | 1950-03-14 | Socony Vacuum Oil Co Inc | Synthetic lubricants |
| US2501349A (en) * | 1946-05-10 | 1950-03-21 | Westinghouse Electric Corp | Insulation for magnetic material |
| US2507956A (en) * | 1947-11-01 | 1950-05-16 | Lithographic Technical Foundat | Process of coating aluminum |
| US2520475A (en) * | 1944-10-06 | 1950-08-29 | Sonnino Carlo | Process for the chemical oxidation of aluminum and alloys thereof |
| US2522474A (en) * | 1942-07-02 | 1950-09-12 | Battelle Memorial Institute | Treatment of zinc surfaces |
| US2559878A (en) * | 1948-12-29 | 1951-07-10 | Western Electric Co | Zinc and cadmium passivating bath |
| US2591479A (en) * | 1947-05-12 | 1952-04-01 | Parker Rust Proof Co | Method of and solution for coating surfaces chiefly of zinc |
| US2681873A (en) * | 1954-02-25 | 1954-06-22 | George L Deniston | Production of black oxide films on aluminum |
| US2762731A (en) * | 1952-03-29 | 1956-09-11 | American Chem Paint Co | Method of and materials for producing paint bonding films on ferriferous metal surfaces |
| US2786002A (en) * | 1954-04-28 | 1957-03-19 | American Chem Paint Co | Method of treating zinciferous surfaces |
| US2795518A (en) * | 1954-04-14 | 1957-06-11 | American Chem Paint Co | Process for treating steel, zinc, and aluminum to increase corrosion resistance |
| US2796370A (en) * | 1955-03-04 | 1957-06-18 | Charles W Ostrander | Composition and method for producing corrosion resistant protective coating on aluminum and aluminum alloys |
| US2796371A (en) * | 1955-03-16 | 1957-06-18 | Allied Res Products Inc | Corrosion resistant protective coating on aluminum and aluminum alloys |
| US2798830A (en) * | 1953-08-04 | 1957-07-09 | American Chem Paint Co | Method of improving the corrosion resistance of certain coated aluminum surfaces |
| US2819192A (en) * | 1955-12-23 | 1958-01-07 | Du Pont | Modification of aluminum surfaces |
| US2843513A (en) * | 1954-07-28 | 1958-07-15 | Allied Res Products Inc | Mixture and method for imparting a corrosion-resistant surface to aluminum, aluminumalloys, and silver |
| US2851386A (en) * | 1954-05-05 | 1958-09-09 | Allied Res Products Inc | Method for coating zinc and zinc alloy sheets |
| US2851385A (en) * | 1952-04-03 | 1958-09-09 | Amchem Prod | Process and composition for coating aluminum surfaces |
| US2864732A (en) * | 1953-10-05 | 1958-12-16 | Battelle Development Corp | Method of coating titanium articles and product thereof |
| US2884350A (en) * | 1955-12-28 | 1959-04-28 | Sylvania Electric Prod | Solderable zinc alloy coating |
| US2926125A (en) * | 1956-03-17 | 1960-02-23 | Canadian Ind | Coating articles of magnesium or magnesium base alloys |
| DE975498C (en) * | 1951-06-27 | 1961-12-14 | American Chem Paint Co | Process to increase the adhesion and service life of organic coatings, e.g. B. of paint, varnish and. Like. On corrosive metal surfaces and solution or concentrate for carrying out the process |
| US3018211A (en) * | 1959-01-26 | 1962-01-23 | Purex Corp Ltd | Composition and process for brightening aluminum and its alloys |
| DE976375C (en) * | 1953-03-10 | 1963-07-25 | Amchem Prod | Process for increasing the corrosion resistance of surfaces made of aluminum and its alloys |
| US3130085A (en) * | 1963-06-04 | 1964-04-21 | Amchem Prod | Method and materials for applying chromate conversion coatings on zinciferous surfaces |
| US3130086A (en) * | 1963-07-22 | 1964-04-21 | Amchem Prod | Materials and method for use in applying chromate conversion coatings on zinciferous surfaces |
| US3347713A (en) * | 1964-02-03 | 1967-10-17 | Hooker Chemical Corp | Process for forming chromate coatings on aluminum |
| US3404046A (en) * | 1964-09-25 | 1968-10-01 | Hooker Chemical Corp | Chromating of zinc and aluminum and composition therefor |
| US3539403A (en) * | 1966-12-07 | 1970-11-10 | Collardin Gmbh Gerhard | Solutions for the deposition of protective layers on zinc surfaces and process therefor |
| US3539402A (en) * | 1967-02-16 | 1970-11-10 | Collardin Gmbh Gerhard | Solutions for the deposition of protective surface layers on iron and zinc and process therefor |
| DE2031358A1 (en) * | 1970-06-25 | 1971-12-30 | Collardin Gmbh Gerhard | Protective coatings on iron, zinc or aluminium - formed by treatment with acid solns contg complex fluorides, free fluorine |
| US3816142A (en) * | 1972-05-08 | 1974-06-11 | K Lindemann | Electroless chromium plating process and composition |
| US3876435A (en) * | 1973-10-01 | 1975-04-08 | Amchem Prod | Chromate conversion coating solutions having chloride, sulfate, and nitrate anions |
| US3982951A (en) * | 1971-09-16 | 1976-09-28 | Stauffer Chemical Company | Aluminum chromate protective coatings for aluminum |
| US4414039A (en) * | 1981-08-21 | 1983-11-08 | Motoren-Und Turbinen-Union Munchen Gmbh | Method of activating titanium surfaces |
| US4551434A (en) * | 1983-03-16 | 1985-11-05 | Mtu Motoren-Und Turbinen-Union Muenchen Gmbh | Method for recognizing structural inhomogeneities in titanium alloy test samples including welded samples |
| US4711667A (en) * | 1986-08-29 | 1987-12-08 | Sanchem, Inc. | Corrosion resistant aluminum coating |
| US4895608A (en) * | 1988-04-29 | 1990-01-23 | Sanchem, Inc. | Corrosion resistant aluminum coating composition |
| US5123978A (en) * | 1991-03-19 | 1992-06-23 | The United States Of America As Represented By The Secretary Of The Navy | Corrosion resistant chromate conversion coatings for heat-treated aluminum alloys |
| US5707465A (en) * | 1996-10-24 | 1998-01-13 | Sanchem, Inc. | Low temperature corrosion resistant aluminum and aluminum coating composition |
| US5769967A (en) * | 1992-04-01 | 1998-06-23 | Henkel Corporation | Composition and process for treating metal |
| US20070119715A1 (en) * | 2005-11-25 | 2007-05-31 | Sacks Abraham J | Corrosion Resistant Wire Products and Method of Making Same |
| KR100777171B1 (en) | 2002-10-15 | 2007-11-16 | 헨켈 코만디트게젤샤프트 아우프 악티엔 | Pickling or brightening/passivating solution and process for steel and stainless steel |
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-
1935
- 1935-09-28 US US42670A patent/US2276353A/en not_active Expired - Lifetime
Cited By (50)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2522474A (en) * | 1942-07-02 | 1950-09-12 | Battelle Memorial Institute | Treatment of zinc surfaces |
| US2434525A (en) * | 1943-08-23 | 1948-01-13 | Rheem Mfg Co | Coating on metals |
| US2434237A (en) * | 1943-09-13 | 1948-01-06 | Sk Wellman Co | Apparatus for applying powdered metal briquets to curved metallic surfaces |
| US2520475A (en) * | 1944-10-06 | 1950-08-29 | Sonnino Carlo | Process for the chemical oxidation of aluminum and alloys thereof |
| US2454799A (en) * | 1944-12-09 | 1948-11-30 | Hart David | Method of producing protective coatings on magnesium powder |
| US2497905A (en) * | 1945-03-03 | 1950-02-21 | Rheem Mfg Co | Coating zinc or cadmium to impart corrosion and abrasion resistance |
| US2501349A (en) * | 1946-05-10 | 1950-03-21 | Westinghouse Electric Corp | Insulation for magnetic material |
| US2591479A (en) * | 1947-05-12 | 1952-04-01 | Parker Rust Proof Co | Method of and solution for coating surfaces chiefly of zinc |
| US2507956A (en) * | 1947-11-01 | 1950-05-16 | Lithographic Technical Foundat | Process of coating aluminum |
| US2559878A (en) * | 1948-12-29 | 1951-07-10 | Western Electric Co | Zinc and cadmium passivating bath |
| US2500672A (en) * | 1949-06-08 | 1950-03-14 | Socony Vacuum Oil Co Inc | Synthetic lubricants |
| DE975498C (en) * | 1951-06-27 | 1961-12-14 | American Chem Paint Co | Process to increase the adhesion and service life of organic coatings, e.g. B. of paint, varnish and. Like. On corrosive metal surfaces and solution or concentrate for carrying out the process |
| US2762731A (en) * | 1952-03-29 | 1956-09-11 | American Chem Paint Co | Method of and materials for producing paint bonding films on ferriferous metal surfaces |
| DE977586C (en) * | 1952-04-03 | 1967-06-08 | Amchem Prod | Process for the production of coatings on aluminum and its alloys |
| US2851385A (en) * | 1952-04-03 | 1958-09-09 | Amchem Prod | Process and composition for coating aluminum surfaces |
| DE976375C (en) * | 1953-03-10 | 1963-07-25 | Amchem Prod | Process for increasing the corrosion resistance of surfaces made of aluminum and its alloys |
| US2798830A (en) * | 1953-08-04 | 1957-07-09 | American Chem Paint Co | Method of improving the corrosion resistance of certain coated aluminum surfaces |
| US2864732A (en) * | 1953-10-05 | 1958-12-16 | Battelle Development Corp | Method of coating titanium articles and product thereof |
| US2681873A (en) * | 1954-02-25 | 1954-06-22 | George L Deniston | Production of black oxide films on aluminum |
| US2795518A (en) * | 1954-04-14 | 1957-06-11 | American Chem Paint Co | Process for treating steel, zinc, and aluminum to increase corrosion resistance |
| US2786002A (en) * | 1954-04-28 | 1957-03-19 | American Chem Paint Co | Method of treating zinciferous surfaces |
| US2851386A (en) * | 1954-05-05 | 1958-09-09 | Allied Res Products Inc | Method for coating zinc and zinc alloy sheets |
| US2843513A (en) * | 1954-07-28 | 1958-07-15 | Allied Res Products Inc | Mixture and method for imparting a corrosion-resistant surface to aluminum, aluminumalloys, and silver |
| US2796370A (en) * | 1955-03-04 | 1957-06-18 | Charles W Ostrander | Composition and method for producing corrosion resistant protective coating on aluminum and aluminum alloys |
| US2796371A (en) * | 1955-03-16 | 1957-06-18 | Allied Res Products Inc | Corrosion resistant protective coating on aluminum and aluminum alloys |
| US2819192A (en) * | 1955-12-23 | 1958-01-07 | Du Pont | Modification of aluminum surfaces |
| US2884350A (en) * | 1955-12-28 | 1959-04-28 | Sylvania Electric Prod | Solderable zinc alloy coating |
| US2926125A (en) * | 1956-03-17 | 1960-02-23 | Canadian Ind | Coating articles of magnesium or magnesium base alloys |
| US3018211A (en) * | 1959-01-26 | 1962-01-23 | Purex Corp Ltd | Composition and process for brightening aluminum and its alloys |
| US3130085A (en) * | 1963-06-04 | 1964-04-21 | Amchem Prod | Method and materials for applying chromate conversion coatings on zinciferous surfaces |
| US3130086A (en) * | 1963-07-22 | 1964-04-21 | Amchem Prod | Materials and method for use in applying chromate conversion coatings on zinciferous surfaces |
| US3347713A (en) * | 1964-02-03 | 1967-10-17 | Hooker Chemical Corp | Process for forming chromate coatings on aluminum |
| US3404046A (en) * | 1964-09-25 | 1968-10-01 | Hooker Chemical Corp | Chromating of zinc and aluminum and composition therefor |
| US3539403A (en) * | 1966-12-07 | 1970-11-10 | Collardin Gmbh Gerhard | Solutions for the deposition of protective layers on zinc surfaces and process therefor |
| US3539402A (en) * | 1967-02-16 | 1970-11-10 | Collardin Gmbh Gerhard | Solutions for the deposition of protective surface layers on iron and zinc and process therefor |
| DE2031358A1 (en) * | 1970-06-25 | 1971-12-30 | Collardin Gmbh Gerhard | Protective coatings on iron, zinc or aluminium - formed by treatment with acid solns contg complex fluorides, free fluorine |
| US3982951A (en) * | 1971-09-16 | 1976-09-28 | Stauffer Chemical Company | Aluminum chromate protective coatings for aluminum |
| US3816142A (en) * | 1972-05-08 | 1974-06-11 | K Lindemann | Electroless chromium plating process and composition |
| US3876435A (en) * | 1973-10-01 | 1975-04-08 | Amchem Prod | Chromate conversion coating solutions having chloride, sulfate, and nitrate anions |
| US4414039A (en) * | 1981-08-21 | 1983-11-08 | Motoren-Und Turbinen-Union Munchen Gmbh | Method of activating titanium surfaces |
| US4551434A (en) * | 1983-03-16 | 1985-11-05 | Mtu Motoren-Und Turbinen-Union Muenchen Gmbh | Method for recognizing structural inhomogeneities in titanium alloy test samples including welded samples |
| US4711667A (en) * | 1986-08-29 | 1987-12-08 | Sanchem, Inc. | Corrosion resistant aluminum coating |
| US4895608A (en) * | 1988-04-29 | 1990-01-23 | Sanchem, Inc. | Corrosion resistant aluminum coating composition |
| US5123978A (en) * | 1991-03-19 | 1992-06-23 | The United States Of America As Represented By The Secretary Of The Navy | Corrosion resistant chromate conversion coatings for heat-treated aluminum alloys |
| US5769967A (en) * | 1992-04-01 | 1998-06-23 | Henkel Corporation | Composition and process for treating metal |
| US5707465A (en) * | 1996-10-24 | 1998-01-13 | Sanchem, Inc. | Low temperature corrosion resistant aluminum and aluminum coating composition |
| KR100777171B1 (en) | 2002-10-15 | 2007-11-16 | 헨켈 코만디트게젤샤프트 아우프 악티엔 | Pickling or brightening/passivating solution and process for steel and stainless steel |
| EP1552035B1 (en) * | 2002-10-15 | 2010-08-25 | Henkel AG & Co. KGaA | Pickling solution and process for stainless steel |
| US20070119715A1 (en) * | 2005-11-25 | 2007-05-31 | Sacks Abraham J | Corrosion Resistant Wire Products and Method of Making Same |
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