US3616308A - Method of producing colored coatings on aluminum - Google Patents
Method of producing colored coatings on aluminum Download PDFInfo
- Publication number
- US3616308A US3616308A US773936A US3616308DA US3616308A US 3616308 A US3616308 A US 3616308A US 773936 A US773936 A US 773936A US 3616308D A US3616308D A US 3616308DA US 3616308 A US3616308 A US 3616308A
- Authority
- US
- United States
- Prior art keywords
- aluminum
- bath
- ions
- article
- alternating current
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 87
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 51
- 238000000576 coating method Methods 0.000 title claims abstract description 40
- -1 aluminum ions Chemical class 0.000 claims abstract description 37
- 239000011248 coating agent Substances 0.000 claims abstract description 34
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- 230000002378 acidificating effect Effects 0.000 claims abstract description 16
- 150000001450 anions Chemical class 0.000 claims abstract description 16
- 238000007743 anodising Methods 0.000 claims abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000001768 cations Chemical class 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 9
- 150000002739 metals Chemical class 0.000 claims abstract description 8
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 8
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 30
- 238000011282 treatment Methods 0.000 claims description 22
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 150000002500 ions Chemical class 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- 239000010949 copper Substances 0.000 claims description 14
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 5
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 claims description 3
- 229940009827 aluminum acetate Drugs 0.000 claims description 3
- 229960000583 acetic acid Drugs 0.000 claims description 2
- 229940046892 lead acetate Drugs 0.000 claims description 2
- AMVQGJHFDJVOOB-UHFFFAOYSA-H aluminium sulfate octadecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O AMVQGJHFDJVOOB-UHFFFAOYSA-H 0.000 claims 3
- 238000004040 coloring Methods 0.000 abstract description 6
- 230000002401 inhibitory effect Effects 0.000 abstract description 2
- 239000003792 electrolyte Substances 0.000 description 14
- 238000004901 spalling Methods 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000010407 anodic oxide Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 239000011669 selenium Substances 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 239000000470 constituent Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 238000007792 addition Methods 0.000 description 5
- 239000003086 colorant Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000000153 supplemental effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 description 1
- 101150052147 ALLC gene Proteins 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- ZPUCINDJVBIVPJ-LJISPDSOSA-N cocaine Chemical compound O([C@H]1C[C@@H]2CC[C@@H](N2C)[C@H]1C(=O)OC)C(=O)C1=CC=CC=C1 ZPUCINDJVBIVPJ-LJISPDSOSA-N 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001254 electrum Inorganic materials 0.000 description 1
- 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 1
- 239000010940 green gold Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- QYHFIVBSNOWOCQ-UHFFFAOYSA-N selenic acid Chemical compound O[Se](O)(=O)=O QYHFIVBSNOWOCQ-UHFFFAOYSA-N 0.000 description 1
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/18—After-treatment, e.g. pore-sealing
- C25D11/20—Electrolytic after-treatment
- C25D11/22—Electrolytic after-treatment for colouring layers
Definitions
- ABSTRACT In procedure for producing colored coatings on aluminum by first anodizing the aluminum surface and then treating such anodically coated surface with alternating current in an acidic bath containing metal ions selected from the group consisting of the following cations and anions: Cu, Ag", Pb, and anions consisting of oxygen combined with one of the metals Se, Te and Mn, to produce a colored deposit in the coating, improved coloring results notably in avoiding or inhibiting occurrence oflocalized nonuniformity, especially with darker or more intense tones, are achieved by maintaining a content of aluminum ions in the bath.
- metal ions selected from the group consisting of the following cations and anions: Cu, Ag", Pb, and anions consisting of oxygen combined with one of the metals Se, Te and Mn
- the present invention relates to a process for producing colored coatings on aluminum, and more particularly relates to the production of inorganic-colored coatings on aluminum articles.
- References to aluminum herein will be understood to include aluminum of ordinary commercial purity and aluminum-base alloys that are suitable for conventional anodizing treatments.
- the term aluminum article as used herein is intended to include semifabricated products, such as rolled aluminum sheet and aluminum extruded sections.
- the present invention relates to improvements in a previously described two-stage process for producing a colored coating which comprises anodically oxidizing an aluminum article and thereafter treating the anodized article by passing an alternating current between such aluminum article and a counterelectrode, while such aluminum article and electrode are immersed in a bath that contains a dissolved compound of a selected metal in an aqueous acidic medium. Under these circumstances the anodic oxide coating on the aluminum article becomes colored. More particularly, the invention is con cerned with such process wherein the acidic bath of the alternating current treatment contains metal ions selected from the group consisting of the following cations and anions: Cu, Agfl Pb. and anions consisting of oxygen combined with one of the metals Se, Te and Mn. Procedures of this sort are included in the description of U.S. Pat. No. 3,382,160, granted May 7, 1968 to Tahei Asada.
- the counterelectrode in the alternating current step may be a material, such as graphite (i.e. carbon), which is inert to the electrolyte, or may be formed of other conductive composition, e.g.
- metal which may advantageously be selected among metals having a solution potential more noble than aluminum in the conventional series of electrode potentials, and which can preferably be the same metal, if available, as constituted by the selected ions in solution in the electrolyte, all as explained in the previous disclosure.
- a graphite or copper counterelectrode may be effectively employed.
- a chief object of the present invention is to reduce the incidence of spalling.
- a further and more specific object is to improve the operation of the above process utilizing metal ions selected from the stated group, notably the second or alternating current treatment stage of such process, so that a full range of tones or shades may be obtained by employing a given bath, including the darker tones that are achieved with higher voltages or longer times or both, while in all cases there is desirable avoidance of deterioration of the colored coating as by spalling or the like.
- the complete procedure includes first anodizing the aluminum surface to produce the anodic coating thereon, and then subjecting the coated surface to alternating current in an aqueous bath containing the selected metal ions, such bath also containing aluminum ions, as for example in amount represented by at least about I gram per liter of aluminum sulfate (calculated as Al,[SO,],.l8l-l,0), or more generally (and approximately) stated at least about ppm. Al ions.
- a typical bath may constitute the salt of the metal selected for coloring function, appropriate acidic and related constituents, and an aluminum compound which in dissolved form is in effect an aluminum salt, advantageously containing an anion otherwise present in the electrolyte.
- a special advantage of the present invention is that a given electrolyte can be employed to provide a wide range of shades or tones, notably up to the darkest values, without difficulty, so that the process has improved flexibility in practice, to accommodate a wide variety of color requirements.
- a given electrolyte can be employed to provide a wide range of shades or tones, notably up to the darkest values, without difficulty, so that the process has improved flexibility in practice, to accommodate a wide variety of color requirements.
- the complete process of producing a colored coating on an aluminum surface of an article involves first anodizing the surface in conventional manner to produce an anodic oxide coating, e.g. of a type customarily applied for protective or like purposes.
- any of a number of known operations may be employed, notably with electrolytes of a group which may be defined as consisting of aqueous solutions of sulfuric acid, chromic acid, or a sulfonic acid such as sulfosalicylic acid, and suitable mixtures of these with other acids or compounds, and while in some cases alternating current anodizing treatment may be feasible, effective results are obtained by anodizing the work with direct current, as for periods of 20 minutes to 60 minutes, in an aqueous solution of sulfuric acid, e.g. 15 percent acid by weight.
- the operating conditions of the anodizing step do not appear to be very critical, being selected largely to suit the thickness and other characteristics of anodic coating desired; the requirements of the subsequent coloring step are satisfied over a considerable range of thicknesses of porous oxide coating on aluminum,
- the second step of the process then involves submerging the anodized aluminum article, if desired afier suitable rinsing, in an acidic bath in which a counterelectrode is likewise submerged, such bath comprising an aqueous acidic solution containing the metal selected for coloring function, specifically metal ions selected from the group consisting of the following cations and anions: Cu, Ag Pb, and anions consisting of oxygen combined with one of the metals Se, Te and Mn.
- alternating current is passed through the solution between the article and the counterelectrode, for sufficient time to effect the desired colored deposit in the oxide coating, e.g. a deposit understood to consist of metal, of the selected ions, which is in chemical combination with oxygen, such as oxide or hydroxide, conveniently herein considered to be oxide.
- the bath should be a water solution containing the metal ions selected for coloring function, and an acidic constituent, the dissolved compounds being all in relatively low concentration.
- the bath constituents including nonmetallic anionic constituents, may be variously selected to provide the desired solubility of metal ions and suitable acidity of the electrolyte, and supplemental or further salts and the like may be incorporated, as desired for supplemental purposes that do not interfere with the formation of the colored deposit, or as may result from initial or subsequent pH adjustment.
- sulfate, borate, acetate, tartrate, phosphate, sulfamate and other common ions have been found appropriate for solutions of one metal or another, e.g.
- salts of the selected metal or as forming the chosen acidic component will depend on solubility and like requirements of the metal ions, as for example in the case of lead ions, substances such as sulfamic acid and acetic acid and their salts should be utilized instead of sulfate.
- the metal ions are of anionic nature, compounds appropriately soluble in the acidic bath should be employed, such as alkali metal selenites, selenium oxide, selenic acid, alkali metal tellurites, permanganates, and the like.
- aluminum is preferably added to the electrolyte in the form of a salt, the anion of which (e.g. sulfate, acetate) is already present in the bath or is otherwise compatible as will be understood or may be readily determined.
- a presently preferred copper electrolyte contains copper sulfate and sulfuric acid, to which the aluminum may be added as aluminum sulfate.
- the aluminum can actually be supplied as a soluble form of aluminum .oxide or aluminum hydroxide, then becoming a corresponding dissolved salt in the presence of acidic constituents. Necessary adjustments of acidity for this and other purposes are made by suitable additions such as sulfuric acid, acetic acid, ammonium hydroxide and the like. While some anions, such as halides (except perhaps chlorides in small concentration) are not presently recommended, the essential requirement is to have dissolved aluminum ions present and selection of a suitable and commonly available salt presents no problem in the light of the foregoing.
- the amount of aluminum present should be sufficient to provide significant inhibition of spalling, i.e. to avoid or materially reduce the occurrence or tendency toward occurrence of minute spots or flaked-off areas, or like spots or defects in the colored product, e.g. in the darker or very dark tones obtainable from the selected metal.
- spalling is often represented by colorless or pale spots, it may sometimes occur otherwise, as for instance where flaking near the outset of the alternating current treatment leads to a more intense tone due to preferential flow of current to the spalled area.
- some utility has been noted for lesser amounts, in general, at least about p.p.m.
- the aluminum compound is added in amount to provide from approximately 1000 to 2500 p.p.m. of al., as for example about 10 to 25 grams per liter of AL ,(SO 1 811,0. Even considerably greater amounts, as up to 40 grams per liter of the aluminum salt (or 4000 ppm. Al), are not believed to be detrimental, so that the upper limit appears primarily economic.
- the anodized article is then suitably rinsed and submerged in the selected acidic bath which contains the appropriate counterelectrode.
- the alter nating current is passed, between the article and the electrode, at a conveniently moderate voltage, say from 5 to 20 volts, for a correspondingly appropriate time, e.g. from a few minutes up to 10 or i5 minutes, sometimes with increasing voltage or other suitable electrical control.
- a conveniently moderate voltage say from 5 to 20 volts
- a correspondingly appropriate time e.g. from a few minutes up to 10 or i5 minutes, sometimes with increasing voltage or other suitable electrical control.
- the shade of color achieved depends on the time of treatment and on electrical conditions; for instance, lighter shades are produced by relatively brief treatment with lower voltages, whereas darker or stronger or very dark colors require a longer time or greater electrical values.
- EXAMPLE 1 Aluminum articles, e.g. aluminum sheets were first anodized as above in the conventional 15 percent sulfuric acid solution for 30 minutes to a film thickness of 0.6 mil, and after rinsing were then subjected to the alternating current treatment, with a counterelectrode of graphite in a copper-containing bath (adjusted to pH about 1.3) having the following composition:
- the treated articles can preferably be subjected to conventional sealing treatment, as in very hot or boiling water, for usual purposes.
- sealing treatment as in very hot or boiling water
- the content of copper salt can be selected over a considerable range, e.g. up to 50 g.p.l., the acid being as required to obtain a preferred pH and the aluminum sulfate being included in amounts, for example, from 2 to 30 g.p.l. or more.
- EXAMPLE 2 Aluminum sheet was first anodized and then subjected to the alternating treatment as in example 1, except that the bath for the latter contained silver and had the following composition:
- EXAMPLE 3 Aluminum sheet was first anodized and then subjected to the alternating treatment as in example 1, except that the bath for the latter contained selenium and had the following composition:
- EXAMPLE 4 Aluminum sheet was first anodized and then subjected to the alternating treatment as in example l, except that the bath for the latter contained tellurium and had the following composition:
- EXAMPLE 5 In this instance aluminum articles were first anodized by conventional treatment as indicated in other examples, and then subjected to the alternating current treatment, with a graphite counterelectrode, in a bath containing from 25 to 30 g.p.l. oflead acetate, 20 to 25 g.p.l. of acetic acid and 20 g.p.l. of aluminum acetate (Allc l-l o j Alternating current was passed at 13 volts for about 5 minutes. A uniform black coating was produced, whereas similar operation without the aluminum addition tended to exhibit some spalling or like difficulty.
- step of adding the aluminum compound consists of adding aluminum sulfate to the bath in amount represented by at least about one gram of Al (SO -l8H O per liter.
- step of adding the aluminum compound consists in adding an aluminum salt to the bath in amount of at least about 2 grams per liter.
- a method of producing an inorganically colored anodic coating on an aluminum surface ofan article wherein said surface has first been anodized to produce an anodic coating thereon and wherein alternating current is passed between said anodized surface and an electrode while both are immersed in an aqueous acidic bath containing metal ions selected from the group consisting anions consisting of oxygen combined with one of the metals Se, Te and Mn, for producing a colored deposit in the coating
- the procedure comprising adding to said bath an aluminum compound in an amount to provide in solution in said bath at least about 200 p.p.m. of aluminum ions and effecting said alternating current treatment while maintaining aluminum ions in said bath in amount of at least about 200 p.p.m.
- a method as defined in claim 10, which comprises adding Al,(SO 'l8I-i O to the bath in amount of at least about l0 grams per liter to provide said aluminum ions.
- a method as defined in claim 7, which includes the step of first anodizing said aluminum surface of the article with direct current between said article as anode and a cathode in an aqueous solution of sulfuric acid to produce said anodic coating.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Chemical Treatment Of Metals (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Cosmetics (AREA)
- Cookers (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB53699/67A GB1241296A (en) | 1967-11-24 | 1967-11-24 | Process for colouring anodised aluminium by electrolytic deposition |
| GB5369867 | 1967-11-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3616308A true US3616308A (en) | 1971-10-26 |
Family
ID=26267320
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US773936A Expired - Lifetime US3616308A (en) | 1967-11-24 | 1968-11-06 | Method of producing colored coatings on aluminum |
| US773935A Expired - Lifetime US3616309A (en) | 1967-11-24 | 1968-11-06 | Method of producing colored coatings on aluminum |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US773935A Expired - Lifetime US3616309A (en) | 1967-11-24 | 1968-11-06 | Method of producing colored coatings on aluminum |
Country Status (17)
| Country | Link |
|---|---|
| US (2) | US3616308A (OSRAM) |
| AT (1) | AT305721B (OSRAM) |
| BE (1) | BE724327A (OSRAM) |
| CH (1) | CH495431A (OSRAM) |
| DE (1) | DE1809741C3 (OSRAM) |
| DK (1) | DK131794C (OSRAM) |
| ES (1) | ES360607A1 (OSRAM) |
| FI (1) | FI47115C (OSRAM) |
| FR (1) | FR1592472A (OSRAM) |
| GB (1) | GB1241296A (OSRAM) |
| IE (1) | IE32543B1 (OSRAM) |
| IL (1) | IL31135A (OSRAM) |
| LU (1) | LU57373A1 (OSRAM) |
| NL (1) | NL141579B (OSRAM) |
| NO (1) | NO120098B (OSRAM) |
| SE (1) | SE337972B (OSRAM) |
| YU (1) | YU34438B (OSRAM) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3772166A (en) * | 1972-07-21 | 1973-11-13 | Perma Technological Ind Inc | Electrolytic process for slating a curvilinear aluminum workpiece |
| US3912602A (en) * | 1973-11-09 | 1975-10-14 | Alusuisse | Process for colouring aluminum electrolytically |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2219437B1 (OSRAM) * | 1973-02-23 | 1975-08-22 | Pechiney Aluminium | |
| US4177299A (en) * | 1978-01-27 | 1979-12-04 | Swiss Aluminium Ltd. | Aluminum or aluminum alloy article and process |
| US4431489A (en) * | 1983-03-31 | 1984-02-14 | Kaiser Aluminum & Chemical Corporation | Coloring process for anodized aluminum products |
| US4931151A (en) * | 1989-04-11 | 1990-06-05 | Novamax Technologies Holdings Inc. | Method for two step electrolytic coloring of anodized aluminum |
| US8050831B2 (en) | 2006-04-07 | 2011-11-01 | Ford Global Technologies, Llc | Vehicle engine speed control for a continuously variable transmission |
| WO2010039937A1 (en) * | 2008-10-01 | 2010-04-08 | Lorin Industries | Outdoor-suitable antique copper color aluminum material and process |
| JP5908266B2 (ja) * | 2011-11-30 | 2016-04-26 | 株式会社Ｓｃｒｅｅｎホールディングス | 陽極化成装置及びそれを備えた陽極化成システム並びに半導体ウエハ |
| US20130153427A1 (en) * | 2011-12-20 | 2013-06-20 | Apple Inc. | Metal Surface and Process for Treating a Metal Surface |
| CN107190299B (zh) * | 2017-06-14 | 2023-07-04 | 江苏昊科汽车空调有限公司 | 用于空调压缩机旋转压缩盘铝合金的硬质氧化方法 |
-
1967
- 1967-11-24 GB GB53699/67A patent/GB1241296A/en not_active Expired
-
1968
- 1968-11-06 US US773936A patent/US3616308A/en not_active Expired - Lifetime
- 1968-11-06 US US773935A patent/US3616309A/en not_active Expired - Lifetime
- 1968-11-12 IE IE1363/68A patent/IE32543B1/xx unknown
- 1968-11-19 DE DE1809741A patent/DE1809741C3/de not_active Expired
- 1968-11-19 FI FI683306A patent/FI47115C/fi active
- 1968-11-21 FR FR1592472D patent/FR1592472A/fr not_active Expired
- 1968-11-21 AT AT1133868A patent/AT305721B/de not_active IP Right Cessation
- 1968-11-21 YU YU2730/68A patent/YU34438B/xx unknown
- 1968-11-22 BE BE724327D patent/BE724327A/xx not_active IP Right Cessation
- 1968-11-22 CH CH1747768A patent/CH495431A/fr not_active IP Right Cessation
- 1968-11-22 DK DK573068A patent/DK131794C/da active
- 1968-11-22 NO NO4668/68A patent/NO120098B/no unknown
- 1968-11-22 LU LU57373D patent/LU57373A1/xx unknown
- 1968-11-22 SE SE15914/68A patent/SE337972B/xx unknown
- 1968-11-22 IL IL31135A patent/IL31135A/en unknown
- 1968-11-22 NL NL686816721A patent/NL141579B/xx not_active IP Right Cessation
- 1968-11-23 ES ES360607A patent/ES360607A1/es not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3772166A (en) * | 1972-07-21 | 1973-11-13 | Perma Technological Ind Inc | Electrolytic process for slating a curvilinear aluminum workpiece |
| US3912602A (en) * | 1973-11-09 | 1975-10-14 | Alusuisse | Process for colouring aluminum electrolytically |
Also Published As
| Publication number | Publication date |
|---|---|
| NL141579B (nl) | 1974-03-15 |
| NO120098B (OSRAM) | 1970-08-24 |
| LU57373A1 (OSRAM) | 1969-03-03 |
| DK131794C (da) | 1976-02-02 |
| DE1809741B2 (OSRAM) | 1971-02-04 |
| IE32543B1 (en) | 1973-09-05 |
| BE724327A (OSRAM) | 1969-05-22 |
| US3616309A (en) | 1971-10-26 |
| AT305721B (de) | 1973-03-12 |
| FI47115C (fi) | 1973-09-10 |
| IL31135A (en) | 1972-10-29 |
| IL31135A0 (en) | 1969-01-29 |
| ES360607A1 (es) | 1970-07-16 |
| IE32543L (en) | 1969-05-24 |
| CH495431A (fr) | 1970-08-31 |
| DE1809741A1 (de) | 1969-11-06 |
| FR1592472A (OSRAM) | 1970-05-11 |
| SE337972B (OSRAM) | 1971-08-23 |
| YU34438B (en) | 1979-07-10 |
| GB1241296A (en) | 1971-08-04 |
| DE1809741C3 (de) | 1975-10-23 |
| DK131794B (da) | 1975-09-01 |
| NL6816721A (OSRAM) | 1969-05-28 |
| FI47115B (OSRAM) | 1973-05-31 |
| YU273068A (en) | 1978-12-31 |
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