US3849263A - Process for electrolytically colouring of aluminium which has previously been anodically oxidized - Google Patents
Process for electrolytically colouring of aluminium which has previously been anodically oxidized Download PDFInfo
- Publication number
- US3849263A US3849263A US00049951A US4995170A US3849263A US 3849263 A US3849263 A US 3849263A US 00049951 A US00049951 A US 00049951A US 4995170 A US4995170 A US 4995170A US 3849263 A US3849263 A US 3849263A
- Authority
- US
- United States
- Prior art keywords
- bath
- article
- aluminium
- tin
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 40
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims description 48
- 238000004040 coloring Methods 0.000 title claims description 25
- 239000004411 aluminium Substances 0.000 title description 34
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 235000011167 hydrochloric acid Nutrition 0.000 claims description 5
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 4
- -1 phenol sulfonic acids Chemical class 0.000 claims description 4
- 239000001119 stannous chloride Substances 0.000 claims description 4
- 235000011150 stannous chloride Nutrition 0.000 claims description 4
- SDGNNLQZAPXALR-UHFFFAOYSA-N 3-sulfophthalic acid Chemical compound OC(=O)C1=CC=CC(S(O)(=O)=O)=C1C(O)=O SDGNNLQZAPXALR-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 claims description 3
- 229910000375 tin(II) sulfate Inorganic materials 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 239000006103 coloring component Substances 0.000 claims description 2
- 230000000536 complexating effect Effects 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 239000011260 aqueous acid Substances 0.000 abstract description 2
- 239000003792 electrolyte Substances 0.000 description 37
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000001117 sulphuric acid Substances 0.000 description 7
- 235000011149 sulphuric acid Nutrition 0.000 description 7
- 229910000906 Bronze Inorganic materials 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000007792 addition Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000010974 bronze Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 5
- 239000004327 boric acid Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- NGPGDYLVALNKEG-UHFFFAOYSA-N azanium;azane;2,3,4-trihydroxy-4-oxobutanoate Chemical compound [NH4+].[NH4+].[O-]C(=O)C(O)C(O)C([O-])=O NGPGDYLVALNKEG-UHFFFAOYSA-N 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910021653 sulphate ion Inorganic materials 0.000 description 4
- 229910001432 tin ion Inorganic materials 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000001419 dependent effect Effects 0.000 description 3
- 239000011133 lead Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000004901 spalling Methods 0.000 description 3
- 150000003606 tin compounds Chemical class 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000001164 aluminium sulphate Substances 0.000 description 2
- 235000011128 aluminium sulphate Nutrition 0.000 description 2
- 238000007743 anodising Methods 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001844 chromium Chemical class 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 235000019646 color tone Nutrition 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 229910052714 tellurium Inorganic materials 0.000 description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000009048 phenolic acids Nutrition 0.000 description 1
- 150000007965 phenolic acids Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 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 v Aluminum is coloured by passing an alternating current between a previously anodized workpiece and a counter electrode in an aqueous acid tin salt.
- the invention relates to a process for electrolytically colouring of aluminium or aluminium alloys which have previously been anodically oxidized.
- the coatings obtained by the process have a uniform colour of good durability.
- aluminium and aluminium alloys which as a matter of ease will also be denoted as aluminium below.
- One of the mostly used methods consists in an immersion of anodically oxidized aluminium in a solution of organic dyes. By this immersion method some inorganic and semi-organic colouring solutions may also be used.
- An immersion of the previously oxidized aluminium into two successive inorganic baths in order to precipitate a coloured insoluble salt in the oxide layer is also known. In the first bath the oxidized aluminium is wetted with a reactant which is then reacted in another bath with a second reactant with formation of an insoluble coloured precipitate in the pores of the oxide layer.
- Processes have also been developed based on a so called integrated colour-anodizing whereby the colour is developed by the formation of compounds due to reaction of alloying elements in the aluminium with the electrolyte, the compounds being precipitated in the alumina layer as it is formed.
- British patent No. 1022927 relates to'a similar process wherein an alternating current is passed between a previously anodically oxidized aluminium article, in order to colour the aluminium article, and a counter electrode of carbon, carborundum or aluminium in an aqueous bath containing a salt yielding a coloured metal oxide or metal hydroxide.
- metal salts in the electrolyte it is suggested to use small amounts of a salt ofnickel, cobalt, chromium, cadmium, vanadium, gold, silver, iron or lead.
- the degree of colouring is on the one hand dependent upon the current density during the second process step and on the other hand upon the duration during the second process step of the treatment in the bath of the aluminium article which has been anodically oxidized in the first process step.
- the known conventional electrolytes e.g. the extended use today of nickel salts (cf. German patent No. 741753, Italian patent No. 338232, Canadian patents Nos. 762991 and 984928 and French patent No. 1477823)
- the current density must be kept as low as possible and it cannot'be increased beyond a certain value as puncture or the known concentric spalling off of the oxide layer will occur.
- the treatment time In order to obtain a sufficient degree of colouring the treatment time must, therefore, be correspondingly increased, and this involves an uneconomic treatment. Further, the duration of the treatment with the alternating current is limited because even at low current densities a too long treatment time will also increase the risk of puncture. It is, accordingly, not automatically possible to increase the degree of colouring as desired.
- the invention relates to a process for electrolytically colouring of aluminium by passing an alternating current, between a previously anodically oxidized aluminium article and a counterelectrode immersed in an acid, aqueous solution of a metal salt, and the process is characterized in that as metal salt a tin salt is used.
- the colours obtained by the present process have essentially bronze tones of varying degrees.
- the counter electrode used in the present process is not decisive, however, it should preferably be made of tin if it is desired continuously to replace the tin ions in the electrolyte which are consumed during the colouring. or of a material which is not attacked by the electrolyte, e.g., stainless steel or titanium, in order to prevent contaminations from being introduced into the electrolyte.
- a counter electrode of aluminium may also be used.
- the counter electrode used in the present process consists preferably of tin or titanium.
- the current density may be strongly increased compared with all other known processes without any risk of puncture arising.
- a doubling of the current density compared with the conventional values is possible without difficulties, and even by a 3 times increase of the current density compared with the permissible values for other known electrolytes for obtaining bronze tones there was not observed any concentric spalling off of the oxide layer.
- Because it is possible in the present process to use a substantially higher current density very dark colour tones are obtained in a relatively short time, and there may e.g. economically and without risk of puncture be obtained a black colour by the use of electrolytes of this invention which are also suited for the production of other colour tones which are acceptable in practice.
- tin salts it has been found particularly advantageous to use stannous chloride and stannous sulphate, and as acid in the electrolyte it has been found advantageous to use hydrochloric acid and sulphuric acid.
- hydrochloric acid and sulphuric acid it has been found advantageous to use hydrochloric acid and sulphuric acid.
- other soluble tin salts and acids may also be used.
- Electrolytic baths which specifically contain tin salts as the compounds to be determining for the properties of the electrolytic bath and the electrolytic colouring have hitherto not been suggested at all'for the second, coloring step of such two-step processes as stated above.
- this effect also occurs in connection with the electrolytic baths used in the present process and which essentially contain a tin salt as metal salt, whereby the electrolytic baths, in spite of their giving a very good colouring, are somewhat unstable.
- a weak organic acid is, therefore, added as a complexforming compound to the acid electrolytic bath containing tin salt and which is used according to the invention.
- the organic acids may e.g. belong to the group consisting of phe nolic acids and sulphonic acids, whereby aromatic radicals attached to the group preferably may from the benzene group.
- the solution becomes more stable, with the additional advantage that the permissible contamination of the bath by aluminium and sodium is strongly increased compared with the otherwise known maximum permissible limits and may be e.g. up to times the values for the hitherto known electrolytes.
- the electrolyte used in the present process is very little sensitive as regards the ratio between the surface of the counter electrode and the aluminium article to be treated and the distance and choice of material for the counter electrode. Due to the good scattering power of the electrolyte the geometrical shape of both the counter electrode and the treated aluminium article is essentially without significance.
- the present process can be carried out by the use of tin salts at a concentration of 0.5 to 20 percent by weight, preferably about 2.0 percent by weight, based on the electrolyte.
- This can preferably have a pH of about 1.5.
- the alternating current can be sinusoidal or have another curve shape and a frequency of 10 to 500 periods per second, preferably technical alternating current of 50 periods per second, and a voltage of 2 to 50 V, preferably 6 V, and there may be used a current density of 0.2 to L0 A/dm, based on the aluminium article. However, this upper limit may be exceeded.
- the electrolytic bath contains sulphuric acid it has been found particularly advantageous when renewing the bath to amend it to a certain degree either by the addition of a certain part of a previously used bath or by direct addition of an amount of aluminium sulphate, e.g. to provide about 50 g aluminium sulphate per liter.
- an amount of aluminium sulphate e.g. to provide about 50 g aluminium sulphate per liter.
- a lower concentration is generally sufficient to ensure a satisfactory colouring of the aluminium article from the beginning.
- the presence-of boric acid is also useful.
- EXAMPLE 2 An aluminium strip which had previously been anodically oxidized for 45 minutes in a 15 percent aqueous solution of sulphuric acid was electrolytically coloured with the use of an alternating current. a counter elec-' trode of stainless steel and an aqueous electrolyte containing 40 ml concentrated HCl per liter and 2.7 percent SnCl per liter. The alternating voltage supplied was at 3 volt and had a frequency of 50 periods per second giving a current density of 0.4 to 0.5 A/dm The colouring process lasted for 10 minutes. and a very attractive brownish black colour was obtained on the aluminium strip. The coating obtained again had a very uniform colour, and this shows that the electrolyte had a good scattering power.
- the aluminium articles were not damaged by the chlorine containing electrolyte for the periods .used, and the corrosion resistance of the coloured coatings was very good after rinsing the aluminium articles with water and sealing of the articles in known manner.
- EXAMPLE 3 There was used an electrolyte consisting of an aqueous solution containing g stannous sulphate per liter, 10 ml concentrated sulphuric acid per liter and l0 ml phenol sulphonic acidas complex-forming compound per liter.
- EXAMPLE 4 There was used an electrolyte consisting of an aqueous solution containing 20 g stannous sulphate per liter, 10 ml concentrated sulphuric acid per liter, 10 g boric acid per liter and 4 to 5 g of an aromatic carboxylic acid, eg sulphophthalic acid. per liter, the carboxylic acid acting as complex-forming compound together with the boric acid.
- an electrolyte consisting of an aqueous solution containing 20 g stannous sulphate per liter, 10 ml concentrated sulphuric acid per liter, 10 g boric acid per liter and 4 to 5 g of an aromatic carboxylic acid, eg sulphophthalic acid. per liter, the carboxylic acid acting as complex-forming compound together with the boric acid.
- EXAMPLE 5 There was used an electrolyte consisting of an aqueous solution containing 20 g stannous sulphate per liter, 10 ml concentrated sulphuric acid per liter, 2 g ammonium tartrate per liter, 10 g boric acid per liter and 4 g of an aromatic carboxylic acid per liter. The addition of the ammonium tartrate improved the conductivity of the electrolyte.
- a process for electrolytically coloring an aluminum article which comprises first, anodically oxidizing said article to form an alumina layer thereon; immersing said article in an aqueous bath comprising a strong acid and a solution of about 0.5 to 20 percent by weight of a divalent tin salt, based on said bath, 'said tin salt being the predominant source of metal ions in said bath capable of forming and determining the color of the colored compounds in said alumina layer, and passing an alternating current between said anodically oxidized article and a counter-electrode via said bath to develop said color on said article.
- said bath includes an aromatic sulfonic acid capable of complexing said tin in divalent form and selected from the group consisting of phenol sulfonic acids and sulfophthalic acid.
- An electrolytic bath for the aluminum coloring process according to claim 1 comprising asolution of a stannous salt in a concentration of 1 percent to 20,
- tin salt is selected from the group consisting of stannous chloride and stannous sulfate.
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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)
- Electroplating And Plating Baths Therefor (AREA)
- Printing Plates And Materials Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NO2638/69A NO120248B (enrdf_load_stackoverflow) | 1969-06-25 | 1969-06-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3849263A true US3849263A (en) | 1974-11-19 |
Family
ID=19878994
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US00049951A Expired - Lifetime US3849263A (en) | 1969-06-25 | 1970-06-25 | Process for electrolytically colouring of aluminium which has previously been anodically oxidized |
Country Status (13)
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3912602A (en) * | 1973-11-09 | 1975-10-14 | Alusuisse | Process for colouring aluminum electrolytically |
| US4014758A (en) * | 1974-04-23 | 1977-03-29 | Pilot Man-Nen-Hitsu Kabushiki Kaisha | Continuous electrolytical treatment of aluminum or its alloys |
| US4128460A (en) * | 1976-09-13 | 1978-12-05 | Daiwa Kasei Kenkyujo Kabushiki Kaisha | Coloring by electrolysis of aluminum or aluminum alloys |
| US4179342A (en) * | 1978-06-28 | 1979-12-18 | Reynolds Metals Company | Coating system method for coloring aluminum |
| US4180443A (en) * | 1978-06-28 | 1979-12-25 | Reynolds Metals Company | Method for coloring aluminum |
| WO1980000158A1 (en) * | 1978-06-28 | 1980-02-07 | Reynolds Metals Co | Coating system |
| US4256546A (en) * | 1977-07-20 | 1981-03-17 | Langbein-Pfanhauser Werke Ag | Method of making a baking form for improved browning of baked goods |
| US4526671A (en) * | 1982-09-24 | 1985-07-02 | Pilot Man-Nen-Hitsu Kabushiki Kaisha | Surface treatment of aluminum or aluminum alloys |
| US4931151A (en) * | 1989-04-11 | 1990-06-05 | Novamax Technologies Holdings Inc. | Method for two step electrolytic coloring of anodized aluminum |
| US5064512A (en) * | 1988-07-19 | 1991-11-12 | Henkel Kommanditgesellschaft Auf Aktien | Process for dyeing anodized aluminum |
| US5538617A (en) * | 1995-03-08 | 1996-07-23 | Bethlehem Steel Corporation | Ferrocyanide-free halogen tin plating process and bath |
| US5658529A (en) * | 1996-03-13 | 1997-08-19 | Johnson & Johnson Medical, Inc. | Method of protecting and sterilizing aluminum surfaces on medical instruments |
| EP3421646A1 (en) | 2017-06-29 | 2019-01-02 | EMPA Eidgenössische Materialprüfungs- und Forschungsanstalt | Colouring method of aluminium alloy member |
| EP4257659A3 (en) * | 2022-04-04 | 2024-02-28 | Samsung Electronics Co., Ltd. | Etching composition, method of etching metal-containing film by using the same, and method of manufacturing semiconductor device by using the same |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT324795B (de) * | 1973-07-02 | 1975-09-25 | Piesslinger Ind Baubedarf | Verfahren und färbeelektrolyt zum graufärben von anodisch oxydierten gegenständen aus aluminium oder dessen legierungen |
| IT1142650B (it) * | 1981-12-31 | 1986-10-08 | Grace Italiana Spa | Impianto e procedimento perfezionato di elettrocolorazione dell'alluminio |
| DE4120415A1 (de) * | 1991-06-20 | 1992-12-24 | Henkel Kgaa | Konfektioniertes zinn(ii)sulfat-granulat zur elektrolytischen metallsalzeinfaerbung |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE741753C (de) * | 1940-04-13 | 1943-11-17 | Langbein Pfanhauser Werke Ag | Verfahren zur elektrolytischen Faerbung von Gegenstaenden aus Aluminium mit oxydischer Oberflaechenschicht |
| US3227639A (en) * | 1961-10-24 | 1966-01-04 | Aluminum Co Of America | Method of anodizing aluminum with electrolyte containing sulfophthalic acid |
| US3382160A (en) * | 1960-03-31 | 1968-05-07 | Asada Tahei | Process for inorganically coloring aluminum |
| US3472744A (en) * | 1965-12-09 | 1969-10-14 | Acorn Anodising Co Ltd | Anodising of aluminium and its alloys |
| US3486991A (en) * | 1965-12-27 | 1969-12-30 | Sumitomo Chemical Co | Method of producing a colored anodic oxide film on aluminum |
-
1969
- 1969-06-25 NO NO2638/69A patent/NO120248B/no unknown
-
1970
- 1970-05-23 DE DE2025284A patent/DE2025284B2/de active Pending
- 1970-06-05 NL NL707008252A patent/NL141580B/xx unknown
- 1970-06-11 ES ES380638A patent/ES380638A1/es not_active Expired
- 1970-06-18 FR FR7022404A patent/FR2047917B1/fr not_active Expired
- 1970-06-18 AT AT547470A patent/AT298924B/de not_active IP Right Cessation
- 1970-06-22 BE BE752359D patent/BE752359A/xx unknown
- 1970-06-22 SE SE08588/70A patent/SE357392B/xx unknown
- 1970-06-24 FI FI701764A patent/FI46987C/fi active
- 1970-06-24 CH CH953570A patent/CH554945A/xx not_active IP Right Cessation
- 1970-06-24 DK DK326970AA patent/DK131243B/da unknown
- 1970-06-25 GB GB3089070A patent/GB1311716A/en not_active Expired
- 1970-06-25 US US00049951A patent/US3849263A/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE741753C (de) * | 1940-04-13 | 1943-11-17 | Langbein Pfanhauser Werke Ag | Verfahren zur elektrolytischen Faerbung von Gegenstaenden aus Aluminium mit oxydischer Oberflaechenschicht |
| US3382160A (en) * | 1960-03-31 | 1968-05-07 | Asada Tahei | Process for inorganically coloring aluminum |
| US3227639A (en) * | 1961-10-24 | 1966-01-04 | Aluminum Co Of America | Method of anodizing aluminum with electrolyte containing sulfophthalic acid |
| US3472744A (en) * | 1965-12-09 | 1969-10-14 | Acorn Anodising Co Ltd | Anodising of aluminium and its alloys |
| US3486991A (en) * | 1965-12-27 | 1969-12-30 | Sumitomo Chemical Co | Method of producing a colored anodic oxide film on aluminum |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3912602A (en) * | 1973-11-09 | 1975-10-14 | Alusuisse | Process for colouring aluminum electrolytically |
| US4014758A (en) * | 1974-04-23 | 1977-03-29 | Pilot Man-Nen-Hitsu Kabushiki Kaisha | Continuous electrolytical treatment of aluminum or its alloys |
| USRE31901E (en) * | 1974-04-23 | 1985-05-28 | Pilot Man-Nen-Hitsu Kabushiki Kaisha | Continuous electrolytical treatment of aluminum or its alloys |
| US4128460A (en) * | 1976-09-13 | 1978-12-05 | Daiwa Kasei Kenkyujo Kabushiki Kaisha | Coloring by electrolysis of aluminum or aluminum alloys |
| US4256546A (en) * | 1977-07-20 | 1981-03-17 | Langbein-Pfanhauser Werke Ag | Method of making a baking form for improved browning of baked goods |
| US4179342A (en) * | 1978-06-28 | 1979-12-18 | Reynolds Metals Company | Coating system method for coloring aluminum |
| WO1980000158A1 (en) * | 1978-06-28 | 1980-02-07 | Reynolds Metals Co | Coating system |
| US4180443A (en) * | 1978-06-28 | 1979-12-25 | Reynolds Metals Company | Method for coloring aluminum |
| US4526671A (en) * | 1982-09-24 | 1985-07-02 | Pilot Man-Nen-Hitsu Kabushiki Kaisha | Surface treatment of aluminum or aluminum alloys |
| US5064512A (en) * | 1988-07-19 | 1991-11-12 | Henkel Kommanditgesellschaft Auf Aktien | Process for dyeing anodized aluminum |
| US4931151A (en) * | 1989-04-11 | 1990-06-05 | Novamax Technologies Holdings Inc. | Method for two step electrolytic coloring of anodized aluminum |
| US5538617A (en) * | 1995-03-08 | 1996-07-23 | Bethlehem Steel Corporation | Ferrocyanide-free halogen tin plating process and bath |
| US5658529A (en) * | 1996-03-13 | 1997-08-19 | Johnson & Johnson Medical, Inc. | Method of protecting and sterilizing aluminum surfaces on medical instruments |
| EP3421646A1 (en) | 2017-06-29 | 2019-01-02 | EMPA Eidgenössische Materialprüfungs- und Forschungsanstalt | Colouring method of aluminium alloy member |
| EP4257659A3 (en) * | 2022-04-04 | 2024-02-28 | Samsung Electronics Co., Ltd. | Etching composition, method of etching metal-containing film by using the same, and method of manufacturing semiconductor device by using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| NO120248B (enrdf_load_stackoverflow) | 1970-09-21 |
| FI46987C (fi) | 1973-08-10 |
| DK131243B (da) | 1975-06-16 |
| DK131243C (enrdf_load_stackoverflow) | 1975-11-17 |
| DE2025284B2 (de) | 1975-08-07 |
| DE2025284A1 (de) | 1971-01-14 |
| FR2047917A1 (enrdf_load_stackoverflow) | 1971-03-19 |
| CH554945A (de) | 1974-10-15 |
| BE752359A (fr) | 1970-12-01 |
| ES380638A1 (es) | 1972-10-01 |
| SE357392B (enrdf_load_stackoverflow) | 1973-06-25 |
| AT298924B (de) | 1972-05-25 |
| FI46987B (enrdf_load_stackoverflow) | 1973-05-02 |
| GB1311716A (en) | 1973-03-28 |
| NL7008252A (enrdf_load_stackoverflow) | 1970-12-29 |
| NL141580B (nl) | 1974-03-15 |
| FR2047917B1 (enrdf_load_stackoverflow) | 1975-11-07 |
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