EP0016298A1 - A solution for imparting tarnish resistance on aluminium surfaces and method for applying it - Google Patents
A solution for imparting tarnish resistance on aluminium surfaces and method for applying it Download PDFInfo
- Publication number
- EP0016298A1 EP0016298A1 EP80100012A EP80100012A EP0016298A1 EP 0016298 A1 EP0016298 A1 EP 0016298A1 EP 80100012 A EP80100012 A EP 80100012A EP 80100012 A EP80100012 A EP 80100012A EP 0016298 A1 EP0016298 A1 EP 0016298A1
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims description 17
- 239000004411 aluminium Substances 0.000 title 1
- 239000000203 mixture Substances 0.000 claims abstract description 38
- -1 lithium silicates Chemical class 0.000 claims abstract description 33
- 229920000620 organic polymer Polymers 0.000 claims abstract description 19
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims abstract description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 12
- 235000014633 carbohydrates Nutrition 0.000 claims abstract description 5
- 150000001720 carbohydrates Chemical class 0.000 claims abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 5
- 235000011007 phosphoric acid Nutrition 0.000 claims abstract description 5
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract description 4
- 150000003016 phosphoric acids Chemical class 0.000 claims abstract description 4
- 150000003460 sulfonic acids Chemical class 0.000 claims abstract description 4
- 150000001408 amides Chemical class 0.000 claims abstract 3
- 239000000243 solution Substances 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 230000007797 corrosion Effects 0.000 claims description 15
- 238000005260 corrosion Methods 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 125000000129 anionic group Chemical group 0.000 claims description 9
- 229920002125 Sokalan® Polymers 0.000 claims description 4
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- 235000019353 potassium silicate Nutrition 0.000 claims description 3
- 229920003169 water-soluble polymer Polymers 0.000 claims description 3
- 239000004111 Potassium silicate Substances 0.000 claims 2
- 239000004115 Sodium Silicate Substances 0.000 claims 2
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 claims 2
- 229910052912 lithium silicate Inorganic materials 0.000 claims 2
- 229910052913 potassium silicate Inorganic materials 0.000 claims 2
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims 2
- 239000010953 base metal Substances 0.000 claims 1
- 229910052914 metal silicate Inorganic materials 0.000 claims 1
- 238000004381 surface treatment Methods 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 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 abstract description 4
- 229910052708 sodium Inorganic materials 0.000 abstract description 4
- 239000011734 sodium Substances 0.000 abstract description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052744 lithium Inorganic materials 0.000 abstract description 3
- 229910052700 potassium Inorganic materials 0.000 abstract description 3
- 239000011591 potassium Substances 0.000 abstract description 3
- 238000005507 spraying Methods 0.000 abstract description 3
- 238000007598 dipping method Methods 0.000 abstract 1
- 238000009877 rendering Methods 0.000 abstract 1
- 238000000576 coating method Methods 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 9
- 239000004615 ingredient Substances 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 5
- 238000002845 discoloration Methods 0.000 description 4
- 150000004760 silicates Chemical class 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 238000007739 conversion coating Methods 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 229910001410 inorganic ion Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000009928 pasteurization Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920000084 Gum arabic Polymers 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000205 acacia gum Substances 0.000 description 2
- 235000010489 acacia gum Nutrition 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000005494 tarnishing Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 244000215068 Acacia senegal Species 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 101100536354 Drosophila melanogaster tant gene Proteins 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229920004890 Triton X-100 Polymers 0.000 description 1
- 239000013504 Triton X-100 Substances 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 235000013334 alcoholic beverage Nutrition 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- YAGKRVSRTSUGEY-UHFFFAOYSA-N ferricyanide Chemical compound [Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YAGKRVSRTSUGEY-UHFFFAOYSA-N 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920005613 synthetic organic polymer Polymers 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 229920003170 water-soluble synthetic polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/60—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 alkaline aqueous solutions with pH greater than 8
- C23C22/66—Treatment of aluminium or alloys based thereon
Definitions
- This invention relates to novel and useful improvements in :hemica1 compositions that impart tarnish and corrosion resistance to metal articles and, in particular, relates to compositions of natter and methods for their application for treating aluminum containers to render them stain and corrosion resistant.
- inorganic ions including chromates and phosphates
- conversion coatings Various corrosion inhibitors have been used commercially such as inorganic ions including chromates and phosphates and are referred to as conversion coatings.
- the surface to be treated is subjected to an aqueous solution containing such ions. It is believed that these inorganic ions or heavy metal ions have the ability to bond or adhere in the form of insoluble oxides which resist tarnishing and corrosion of the metal surface.
- the conversion coating solution is prepared and sprayed at some elevated temperature for a short period of time. After treating the metal surface with the solution, the surface is thoroughly rinsed with water to remove unreacted coating solution.
- Still a further object of this invention is that it provides aqueous coating solutions which are free of toxic materials and which are capable of forming on an aluminum surface a uniformly clear and colorless coating.
- a solution for surface treating a metal to render the surface thereof tarnish and corrosion resistant comprising an alkali metal silicate and a water-soluble organic polymer having displaceable hydrogens or displaced hydrogens.
- the instant invention also relates to treating aluminum surfaces, the surfaces being protected against tarnish and corrosion by applying a solution comprising alkali metal silicates, a water-soluble organic polymer having displaceable hydrogens or displaced hydrogens and water.
- compositions herein do not present toxic materials and do not have any disposal problems.
- the subject compositions are free of chromium ions and of the chromium subgroup of the Periodic Table and also materials such as ferricyanide and ferrocyanide.
- silicates such as sodium, potassium or lithium, or mixtures of such silicates.
- These silicates are known generally as water glasses and are usually aqueous solutions containing numerous varieties of alkali metal silicates, e.g., and may be represented generally as where M is sodium, potassium or lithium and x is an integer, generally between 1 and 10.
- these aqueous silicate solutions have a specific gravity range from about 1.3 to about 1.6 and comprise about 23 to about 48 percent by weight of the alkali metal silicate.
- Effective silica to metal oxide weight ratios range from about 1.87 to about 10.0.
- the useful polymers of the subject invention are organic, polymeric substances having displaceable or displaced hydrogens and are generally derived by polymerization of at least one monoolefinic compound through an aliphatic unsaturated group to yield a water-soluble synthetic polymer having a structure substantially free of cross-linkage.
- the polymers herein are those water-soluble polymers having a linear polymeric structure of carbon or carbon with some other atom such as oxygen and contain in a pendent side chain a hydrophilic group from the class consisting of hydroxyl, carboxylic acids, carboxylic acid amides, sulfonic acids and phosphoric acids.
- the aforementioned polymers fall into two classes, 1) those consisting of polymeric organic substances which in an queous medium will form organic anions having a substantial number of negative charges distributed at a multiplicity of positions In the polymer, and (2) those consisting of polymeric organic substances which in an aqueous medium will not form ions but nonetheless contain a sufficient number of hydrophilic groups to be vater-soluble.
- the first class of polymers may be referred to as anionic organic polymers and the second class may be called non-ionic-organic polymers.
- composition herein may be readily formulated in an aqueous media.
- the organic and inorganic ingredients may be mixed in any order into water.
- the compositions are prepared by mixing the components in a given amount of water with constant stirring within ambient temperatures until the ingredients go fully into solution.
- the preferred range for both the alkali metal silicates and soluble polymers should be between about 0.05 and about 5 weight percent. At its most preferred embodiment a mixture of the alkali metal silicate and soluble polymer should be present at about 3 weight percent based on the total weight of the solution. Lower concentrations do not produce an appreciable improvement in corrosion characteristics, and higher concentrations do not increase these characteristics, generally, any further.
- To these compositions may be readily added other various ingredients that are compatible with the system. Such ingredients include wetting agents, dyes, pigments and germacides.
- the compositions herein described and claimed may be readily applied by various conventional means known to the art and including di . pping, spraying, immersion, and roll-on techniques. It is believed that the compositions herein can be readily applied most economically and effectively by spraying.
- the temperature of the solutiori will normally be from 30 to 90°C., preferably about 35 to about 60°C., and the contact time will be between about 15 and 90 seconds and usually less than 70 seconds.
- Two commercial formulations were also tested as indicated in the table. The ratings in the respective columns represent the amount of discoloration for each example.
- aqueous coating solutions containing an alkali metal silicate and a water-soluble organic polymer of the anionic, non-ionic type or mixtures thereof are effective in protecting aluminum surfaces.
- the corrosion resis - tant properties of the coating formed by applications of such solutions within the scope of the present invention include the ability of the coating to withstand blackening or other discoloration when subjected to boiling water for a period of time of at least two minutes or longer.
- compositions of the present invention can be used to protect pure aluminum or alloys of aluminum, for example, aluminum alloys containing minor amounts of metals such as, for example, magnesium, manganese, copper and silicon.
- the surfaces may be dried by conventional means such as an oven having forced circulation of hot air. After the coating has dried it can be readily subjected to lacquering or to decorative operations which can include applying to the surfaces inks, paints or other resin coating. With the methods and compositions of this invention very excellent adhesion of these decorative finishes is realized.
- non-ionic polymers examples include poly(vinyl alcohol), poly(acrylamide) and a number of organic polymeric coagulants of vegetable and cellulosic origin including Gum Arabic.
- anionic types are poly(acrylic-co-acrylate), poly(acrylic acid), poly(maleic anhydride-co-methylvinyl ether), poly(styrene sulfonic acid), sodium poly(acrylate), sodium poly(methacrylate), poly(itaconic- co-vinyl acetate) and the like.
- poly(acrylic-co-acrylate) is meant those copolymers of acrylic acid, methacrylic acid, methyl methacrylate, methylacrylate and derivatives thereof.
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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)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
Description
- This invention relates to novel and useful improvements in :hemica1 compositions that impart tarnish and corrosion resistance to metal articles and, in particular, relates to compositions of natter and methods for their application for treating aluminum containers to render them stain and corrosion resistant.
- As is known, when metal surfaces are exposed to hot aqueous solutions, especially aluminum surfaces, for extended periods of time there is a marked tendency for such surfaces to tarnish to a brown or black coloration. Apparently, this coloration is a refractive effect of the light as it passes through amorphous platelets of generally hydrated aluminum oxides that deposit and build up on the surface of the metal. This problem becomes acute in certain industries. For example, it has been the general practice in breweries to pasteurize alcoholic beverages such as ale, stout and beer in metal containers and this is generally done by subjecting the cans to hot water baths or sprays in the range of about 140°F to about 170°F. In subjecting metal containers to hot water there is a marked tendency for the metal surface, especially aluminum, to stain upon exposure and this is especially noted on the bottom portions of the containers. In practice, the severest problem of staining or discoloration is encountered during pasteurizing of the package as no organic coating is applied to the container bottom to protect it from corrosion and if left untreated, it will discolor during pasteurization, turning brownish. While seemingly this effect does not harm the contents thereof, it makes the product unappealing in its appearance to the consumer. Heretofore it has been a practice in the art to apply a so-called conversion coating to metal containers in order to suppress or passivate such metal and to prevent tarnishing as well as to promote the adhesion of inner lacquers and outer coatings of ink, paints and the like.
- Various corrosion inhibitors have been used commercially such as inorganic ions including chromates and phosphates and are referred to as conversion coatings. Generally, the surface to be treated is subjected to an aqueous solution containing such ions. It is believed that these inorganic ions or heavy metal ions have the ability to bond or adhere in the form of insoluble oxides which resist tarnishing and corrosion of the metal surface. In general, the conversion coating solution is prepared and sprayed at some elevated temperature for a short period of time. After treating the metal surface with the solution, the surface is thoroughly rinsed with water to remove unreacted coating solution. However, in spite of the advantages of these corrosion inhibiting solutions, these inorganic ions have come under increasing scruti- nization by environmental groups and governmental agencies with the result that there has been an increasing demand for compositions that do not have these detrimental heavy metal ions.
- It is accordingly an object of the present invention to provide a composition of matter that offers stain and tarnish resistance to metal substrates, the composition of matter having absent therefrom any heavy metal ions.
- It is another principal object of the instant invention to provide a method of passivating metallic surfaces to render such surfaces stain and corrosion resistant by means of aqueous solutions having small but effective concentrations of ingredients which are not detrimental to the environment.
- It is still another object of the subject invention to provide means for protecting surfaces of aluminum and aluminum base stock against tarnish and corrosion and at the same time enhancing the same for receiving other coatings thereon.
- Still a further object of this invention is that it provides aqueous coating solutions which are free of toxic materials and which are capable of forming on an aluminum surface a uniformly clear and colorless coating.
- It is still a further object of this invention to provide novel compositions of matter that protect surfaces of aluminum from blackening or other discoloration when exposed to hot or boiling water, especially during pasteurization processes associated with aluminum containers.
- These and other objects of the invention will become more readily apparent from a review and study of the specification, including the examples and claims herein.
- Briefly, in accordance with this invention, a solution for surface treating a metal to render the surface thereof tarnish and corrosion resistant is described and claimed, said solution comprising an alkali metal silicate and a water-soluble organic polymer having displaceable hydrogens or displaced hydrogens. The instant invention also relates to treating aluminum surfaces, the surfaces being protected against tarnish and corrosion by applying a solution comprising alkali metal silicates, a water-soluble organic polymer having displaceable hydrogens or displaced hydrogens and water.
- Metal surfaces treated by the process of this invention remain stain and corrosion resistant over a long period of time and do not have to be futher treated or coated. Furthermore, the compositions herein do not present toxic materials and do not have any disposal problems. Thus, the subject compositions are free of chromium ions and of the chromium subgroup of the Periodic Table and also materials such as ferricyanide and ferrocyanide.
- The particular group of silicates that have been found to be effective herein are those aqueous silicates such as sodium, potassium or lithium, or mixtures of such silicates. These silicates are known generally as water glasses and are usually aqueous solutions containing numerous varieties of alkali metal silicates, e.g.,
- In general these aqueous silicate solutions have a specific gravity range from about 1.3 to about 1.6 and comprise about 23 to about 48 percent by weight of the alkali metal silicate. Effective silica to metal oxide weight ratios range from about 1.87 to about 10.0.
- The useful polymers of the subject invention are organic, polymeric substances having displaceable or displaced hydrogens and are generally derived by polymerization of at least one monoolefinic compound through an aliphatic unsaturated group to yield a water-soluble synthetic polymer having a structure substantially free of cross-linkage. In general, the polymers herein are those water-soluble polymers having a linear polymeric structure of carbon or carbon with some other atom such as oxygen and contain in a pendent side chain a hydrophilic group from the class consisting of hydroxyl, carboxylic acids, carboxylic acid amides, sulfonic acids and phosphoric acids. It will be appreciated that in its broadest aspect the aforementioned polymers fall into two classes, 1) those consisting of polymeric organic substances which in an queous medium will form organic anions having a substantial number of negative charges distributed at a multiplicity of positions In the polymer, and (2) those consisting of polymeric organic substances which in an aqueous medium will not form ions but nonetheless contain a sufficient number of hydrophilic groups to be vater-soluble. The first class of polymers may be referred to as anionic organic polymers and the second class may be called non-ionic-organic polymers.
- Very small concentrations of the ingredients herein defined have been found effecitve for improving the corrosion resistance. The synthetic organic polymers containing only carboxylic acid, sulfonic acid, phosphoric acid, as well as the salts thereof in a side chain are anionic and those that contain hydroxy and carboxylic acid amide in the side chain are non-ionic. Natural carbohydrates have been found effective herein and included the highly branched polymers of acacia gum. The invention herein contemplates polymers that contain either the anionic or non-ionic groups as well as mixtures thereof.
- The composition herein may be readily formulated in an aqueous media. The organic and inorganic ingredients may be mixed in any order into water. Preferably, the compositions are prepared by mixing the components in a given amount of water with constant stirring within ambient temperatures until the ingredients go fully into solution.
- The preferred range for both the alkali metal silicates and soluble polymers should be between about 0.05 and about 5 weight percent. At its most preferred embodiment a mixture of the alkali metal silicate and soluble polymer should be present at about 3 weight percent based on the total weight of the solution. Lower concentrations do not produce an appreciable improvement in corrosion characteristics, and higher concentrations do not increase these characteristics, generally, any further. To these compositions may be readily added other various ingredients that are compatible with the system. Such ingredients include wetting agents, dyes, pigments and germacides. The compositions herein described and claimed may be readily applied by various conventional means known to the art and including di.pping, spraying, immersion, and roll-on techniques. It is believed that the compositions herein can be readily applied most economically and effectively by spraying.
- The following tabulation gives Examples comprising compositions as defined herein that were prepared with the amount indicated in grams per liter for the ingredients. To each of Examples 8-20 were added about 0.01 grams of a commercial wetting agent, Triton X-100. Each formulation was placed in contact with an aluminum coupon for about two (2) minutes, at the temperature indicated and thereafter rinsed and dried. The thus-treated coupons were thereafter submerged for fifteen (15) minutes at about 75°C., in a standard solution comprising an aqueous solution of 220 ppm NaNCO3 and 83 ppm NaCL. The processing conditions of temperature, contact time, and contact method are interdependent. In general, application of the compositions herein is conventionally by spray technique and, considering normal plant operations, the temperature of the solutiori will normally be from 30 to 90°C., preferably about 35 to about 60°C., and the contact time will be between about 15 and 90 seconds and usually less than 70 seconds. Two commercial formulations were also tested as indicated in the table. The ratings in the respective columns represent the amount of discoloration for each example.
- It will be appreciated that is has been found in accordance with the present invention that aqueous coating solutions containing an alkali metal silicate and a water-soluble organic polymer of the anionic, non-ionic type or mixtures thereof are effective in protecting aluminum surfaces. The corrosion resis- tant properties of the coating formed by applications of such solutions within the scope of the present invention include the ability of the coating to withstand blackening or other discoloration when subjected to boiling water for a period of time of at least two minutes or longer.
- The particular compositions of the present invention can be used to protect pure aluminum or alloys of aluminum, for example, aluminum alloys containing minor amounts of metals such as, for example, magnesium, manganese, copper and silicon. Presently, two of the most common alloys used in the aluminum container industry are aluminum alloys 3003 and 3004.
- After the coating compositions are applied the surfaces may be dried by conventional means such as an oven having forced circulation of hot air. After the coating has dried it can be readily subjected to lacquering or to decorative operations which can include applying to the surfaces inks, paints or other resin coating. With the methods and compositions of this invention very excellent adhesion of these decorative finishes is realized.
- A large number of water-soluble polymers of both the anionic and non-ionic type may be readily employed. Illustrative of the non-ionic polymers are poly(vinyl alcohol), poly(acrylamide) and a number of organic polymeric coagulants of vegetable and cellulosic origin including Gum Arabic. Illustrative of the anionic types are poly(acrylic-co-acrylate), poly(acrylic acid), poly(maleic anhydride-co-methylvinyl ether), poly(styrene sulfonic acid), sodium poly(acrylate), sodium poly(methacrylate), poly(itaconic- co-vinyl acetate) and the like.
-
- There has been disclosed herein a method of and a composition for treating aluminum metal surfaces, and in particular those metal surfaces that are subjected to hot water solutions and the like, especially in pasteurization processes for aluminum can bodies. In view of the specifications, those skilled in the art may have many modifications which fall within the true spirit and scope of this invention. It is intended that all such modifications be within the scope of the appended claim.
Claims (20)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT80100012T ATE4465T1 (en) | 1979-01-22 | 1980-01-03 | A SOLUTION TO PREVENT TARNISHING OF ALUMINUM SURFACES AND HOW TO APPLY IT. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US528079A | 1979-01-22 | 1979-01-22 | |
US5280 | 2004-12-06 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0016298A1 true EP0016298A1 (en) | 1980-10-01 |
EP0016298B1 EP0016298B1 (en) | 1983-08-17 |
Family
ID=21715108
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP80100012A Expired EP0016298B1 (en) | 1979-01-22 | 1980-01-03 | A solution for imparting tarnish resistance on aluminium surfaces and method for applying it |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0016298B1 (en) |
JP (1) | JPS55119179A (en) |
AT (1) | ATE4465T1 (en) |
DE (1) | DE3064550D1 (en) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4492616A (en) * | 1982-09-01 | 1985-01-08 | Hoechst Aktiengesellschaft | Process for treating aluminum oxide layers and use in the manufacture of offset-printing plates |
EP0240940A2 (en) * | 1986-04-03 | 1987-10-14 | Showa Aluminum Corporation | Composition for forming hydrophilic film on aluminum |
US5518555A (en) * | 1993-08-16 | 1996-05-21 | Betz Laboratories, Inc. | Chromium and fluoride free metal treatment |
DE19518514A1 (en) * | 1995-05-19 | 1996-11-21 | Setral Chemie Technology Gmbh | Corrosion inhibitor for use in aq. media |
WO1999066104A2 (en) * | 1998-06-19 | 1999-12-23 | Alcoa Inc. | Method for inhibiting stains on aluminum product surfaces |
EP1221497A2 (en) * | 1998-06-19 | 2002-07-10 | Alcoa Inc. | Method for inhibiting stains on aluminum product surfaces |
FR2837218A1 (en) * | 2002-03-18 | 2003-09-19 | Dacral Sa | Anti-corrosion, lubricating and/or anti-fingerprint coating composition for zinc- or aluminum-coated metal, e.g. galvanised steel, contains sodium, potassium or lithium silicate, optionally surfactant, and water |
CN115305464A (en) * | 2022-08-23 | 2022-11-08 | 江门市安诺特炊具制造有限公司 | Surface treatment method of aluminum alloy cooker and aluminum alloy cooker |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001164175A (en) * | 1999-12-09 | 2001-06-19 | Kansai Paint Co Ltd | Hydrophilifying agent for heat-exchanger fin material |
JP4558875B2 (en) * | 1999-12-21 | 2010-10-06 | 関西ペイント株式会社 | Hydrophilic composition for heat exchanger fin material |
KR100376561B1 (en) * | 2000-07-11 | 2003-03-17 | 지성규 | Manufacturing Method for Coating Aluminium Plate and Coating Method Using Thereof |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE871239C (en) * | 1951-06-08 | 1953-03-19 | Basf Ag | Process for the production of a dense, fine-grained coating on objects made of aluminum or aluminum alloys |
FR1204092A (en) * | 1957-10-08 | 1960-01-22 | Ca Atomic Energy Ltd | Improvements in the protection of aluminum alloys against corrosion |
FR1381908A (en) * | 1963-02-07 | 1964-12-14 | Alusuisse | Method of protecting the surface of aluminum containers to be sterilized |
US3175931A (en) * | 1963-11-26 | 1965-03-30 | Carl A Burgess | Treatment of aluminum surfaces |
US3297616A (en) * | 1963-12-02 | 1967-01-10 | Koppers Co Inc | Self-curing silicate and acrylate coatings |
US3450661A (en) * | 1964-07-28 | 1969-06-17 | Progil | Acrylo-silicate binders for coating compositions |
GB1402880A (en) * | 1971-08-05 | 1975-08-13 | Chemed Corp | Corrosion inhibition |
-
1980
- 1980-01-03 DE DE8080100012T patent/DE3064550D1/en not_active Expired
- 1980-01-03 EP EP80100012A patent/EP0016298B1/en not_active Expired
- 1980-01-03 AT AT80100012T patent/ATE4465T1/en not_active IP Right Cessation
- 1980-01-22 JP JP533480A patent/JPS55119179A/en active Pending
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE871239C (en) * | 1951-06-08 | 1953-03-19 | Basf Ag | Process for the production of a dense, fine-grained coating on objects made of aluminum or aluminum alloys |
FR1204092A (en) * | 1957-10-08 | 1960-01-22 | Ca Atomic Energy Ltd | Improvements in the protection of aluminum alloys against corrosion |
FR1381908A (en) * | 1963-02-07 | 1964-12-14 | Alusuisse | Method of protecting the surface of aluminum containers to be sterilized |
US3175931A (en) * | 1963-11-26 | 1965-03-30 | Carl A Burgess | Treatment of aluminum surfaces |
US3297616A (en) * | 1963-12-02 | 1967-01-10 | Koppers Co Inc | Self-curing silicate and acrylate coatings |
US3450661A (en) * | 1964-07-28 | 1969-06-17 | Progil | Acrylo-silicate binders for coating compositions |
GB1402880A (en) * | 1971-08-05 | 1975-08-13 | Chemed Corp | Corrosion inhibition |
Non-Patent Citations (1)
Title |
---|
CORROSION, Vol. 18, No. 4, April 1962, pages 143-153 D.G. ALTENPOHL: "Use of Boehmite Films For Corrosion Protection of Aluminum". * |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4492616A (en) * | 1982-09-01 | 1985-01-08 | Hoechst Aktiengesellschaft | Process for treating aluminum oxide layers and use in the manufacture of offset-printing plates |
EP0240940A2 (en) * | 1986-04-03 | 1987-10-14 | Showa Aluminum Corporation | Composition for forming hydrophilic film on aluminum |
EP0240940A3 (en) * | 1986-04-03 | 1989-09-06 | Showa Aluminum Corporation | Composition for forming hydrophilic film on aluminum |
US5518555A (en) * | 1993-08-16 | 1996-05-21 | Betz Laboratories, Inc. | Chromium and fluoride free metal treatment |
DE19518514A1 (en) * | 1995-05-19 | 1996-11-21 | Setral Chemie Technology Gmbh | Corrosion inhibitor for use in aq. media |
WO1999066104A3 (en) * | 1998-06-19 | 2000-03-30 | Alcoa Inc | Method for inhibiting stains on aluminum product surfaces |
WO1999066104A2 (en) * | 1998-06-19 | 1999-12-23 | Alcoa Inc. | Method for inhibiting stains on aluminum product surfaces |
EP1221497A2 (en) * | 1998-06-19 | 2002-07-10 | Alcoa Inc. | Method for inhibiting stains on aluminum product surfaces |
EP1221497A3 (en) * | 1998-06-19 | 2003-12-03 | Alcoa Inc. | Method for inhibiting stains on aluminum product surfaces |
FR2837218A1 (en) * | 2002-03-18 | 2003-09-19 | Dacral Sa | Anti-corrosion, lubricating and/or anti-fingerprint coating composition for zinc- or aluminum-coated metal, e.g. galvanised steel, contains sodium, potassium or lithium silicate, optionally surfactant, and water |
WO2003078683A2 (en) * | 2002-03-18 | 2003-09-25 | Dacral | Coating composition for a metal substrate |
WO2003078683A3 (en) * | 2002-03-18 | 2004-06-03 | Dacral | Coating composition for a metal substrate |
US7232479B2 (en) | 2002-03-18 | 2007-06-19 | Dacral | Coating composition for a metal substrate |
CN115305464A (en) * | 2022-08-23 | 2022-11-08 | 江门市安诺特炊具制造有限公司 | Surface treatment method of aluminum alloy cooker and aluminum alloy cooker |
CN115305464B (en) * | 2022-08-23 | 2024-02-06 | 江门市安诺特炊具制造有限公司 | Surface treatment method of aluminum alloy cooker and aluminum alloy cooker |
Also Published As
Publication number | Publication date |
---|---|
JPS55119179A (en) | 1980-09-12 |
EP0016298B1 (en) | 1983-08-17 |
ATE4465T1 (en) | 1983-09-15 |
DE3064550D1 (en) | 1983-09-22 |
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