NO131208B - - Google Patents
Download PDFInfo
- Publication number
- NO131208B NO131208B NO0693/73A NO69373A NO131208B NO 131208 B NO131208 B NO 131208B NO 0693/73 A NO0693/73 A NO 0693/73A NO 69373 A NO69373 A NO 69373A NO 131208 B NO131208 B NO 131208B
- Authority
- NO
- Norway
- Prior art keywords
- sealing
- acid
- carried out
- solutions containing
- hydrogen atom
- Prior art date
Links
- 238000000034 method Methods 0.000 claims description 27
- 238000007789 sealing Methods 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 23
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 150000003009 phosphonic acids Chemical class 0.000 claims description 11
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 9
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 229920001353 Dextrin Polymers 0.000 claims description 7
- 239000004375 Dextrin Substances 0.000 claims description 7
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims description 7
- 229910001424 calcium ion Inorganic materials 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 235000019425 dextrin Nutrition 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 229910000838 Al alloy Inorganic materials 0.000 claims description 4
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical group [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims 2
- PAXPHUUREDAUGV-UHFFFAOYSA-N OP(=O)OP(O)(O)=O Chemical compound OP(=O)OP(O)(O)=O PAXPHUUREDAUGV-UHFFFAOYSA-N 0.000 claims 1
- 238000000576 coating method Methods 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229940120146 EDTMP Drugs 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000010407 anodic oxide Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- GPCTYPSWRBUGFH-UHFFFAOYSA-N (1-amino-1-phosphonoethyl)phosphonic acid Chemical compound OP(=O)(O)C(N)(C)P(O)(O)=O GPCTYPSWRBUGFH-UHFFFAOYSA-N 0.000 description 1
- LBPHBRVNBKGYTP-UHFFFAOYSA-N (1-hydroxy-1-phosphonohexyl)phosphonic acid Chemical compound CCCCCC(O)(P(O)(O)=O)P(O)(O)=O LBPHBRVNBKGYTP-UHFFFAOYSA-N 0.000 description 1
- XHAZMZWXAOBLQG-UHFFFAOYSA-N (1-hydroxy-1-phosphonopropyl)phosphonic acid Chemical compound CCC(O)(P(O)(O)=O)P(O)(O)=O XHAZMZWXAOBLQG-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 1
- 229910000789 Aluminium-silicon alloy Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-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
- DJEQZVQFEPKLOY-UHFFFAOYSA-N N,N-dimethylbutylamine Chemical compound CCCCN(C)C DJEQZVQFEPKLOY-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical class OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- YVIMHTIMVIIXBQ-UHFFFAOYSA-N [SnH3][Al] Chemical compound [SnH3][Al] YVIMHTIMVIIXBQ-UHFFFAOYSA-N 0.000 description 1
- BFDMEODWJJUORJ-UHFFFAOYSA-N [dimethylamino(phosphono)methyl]phosphonic acid Chemical compound CN(C)C(P(O)(O)=O)P(O)(O)=O BFDMEODWJJUORJ-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 159000000011 group IA salts Chemical class 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- DAZXVJBJRMWXJP-UHFFFAOYSA-N n,n-dimethylethylamine Chemical compound CCN(C)C DAZXVJBJRMWXJP-UHFFFAOYSA-N 0.000 description 1
- GNVRJGIVDSQCOP-UHFFFAOYSA-N n-ethyl-n-methylethanamine Chemical compound CCN(C)CC GNVRJGIVDSQCOP-UHFFFAOYSA-N 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- MYHXWQZHYLEHIU-UHFFFAOYSA-N oxalic acid;sulfuric acid Chemical compound OS(O)(=O)=O.OC(=O)C(O)=O MYHXWQZHYLEHIU-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000008234 soft water Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229950000244 sulfanilic acid Drugs 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 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
- C25D11/24—Chemical after-treatment
- C25D11/246—Chemical after-treatment for sealing layers
Description
Fremgangsmåte til behandling av Procedure for treatment of
aluminiumoverflater ved oksydasjon aluminum surfaces by oxidation
med etterfølgende tetning. with subsequent sealing.
Oppfinnelsen vedrører en fremgangsmåte til behandling The invention relates to a method for treatment
av overflater av aluminium eller aluminiumlegeringer ved anodisk frembringelse av oksydsjikt med etterfølgende tetning i vandig oppløsning ved forhøyede temperaturer. Derved hindres ved tilsetning av bestemte fosfonsyrer dannelsen av forstyrrende aluminiumhydroksyd-belegg (sealingbelegg) på overflaten, samt det unngås vanskeligheter ved vannets hårdhetssalter, of surfaces of aluminum or aluminum alloys by anodic production of an oxide layer with subsequent sealing in aqueous solution at elevated temperatures. By adding specific phosphonic acids, the formation of disruptive aluminum hydroxide coatings (sealing coatings) on the surface is thereby prevented, and difficulties with water hardness salts are avoided,
På aluminiumoverflater påføres for korrosjonsbeskyttelse ofte anodisk frembragte oksydsjikt. Disse oksydsjikt beskytter aluminiumoverflåtene for innvirkning av klimapåvirkning og andre korroderende medier. Videre påføres også de anodiske oksydsjikt for å få en hårdere overflate og dermed oppnå en høyere slitasje-fasthet av aluminium. Ved oksydsjiktenes egenfarge resp, deres delvis lett fargbarhet lar det seg oppnå spesielt dekorative effekter. Anodically produced oxide layers are often applied to aluminum surfaces for corrosion protection. These oxide layers protect the aluminum surfaces from the effects of climatic influences and other corrosive media. Furthermore, the anodic oxide layer is also applied to obtain a harder surface and thus achieve a higher wear resistance of aluminium. Particularly decorative effects can be achieved through the oxide layers' own color or, in part, their light colorability.
For påføring av anodiske oksydsjikt på aluminium er For the application of anodic oxide layers on aluminum is
det kjent en rekke fremgangsmåter. Eksempelvis foregår - frembringel-sen av oksydsjikt med likestrøm i oppløsninger av svovelsyre (like-strøm-svovelsyre-fremgangsmåten). Ofte anvendes imidlertid oppløs-ninger av organiske syrer som spesielt sulfoftalsyre resp. sulfanil-syre eller også disse i blanding med svovelsyre. Sistnevnte fremgangsmåter er spesielt kjent som Autocolor-fremgangsmåten. a number of methods are known. For example - the production of an oxide layer takes place with direct current in solutions of sulfuric acid (the direct current sulfuric acid method). Often, however, solutions of organic acids such as sulfophthalic acid or sulphanilic acid or these in a mixture with sulfuric acid. The latter methods are particularly known as the Autocolor method.
Disse anodisk påførte oksydsjikt oppfyller imidlertid ikke alle krav med hensyn til korrosjons-beskyttelse da de har en porøs struktur. Av denne grunn er det nødvendig å ettertette oksyd-sjiktene. Denne ettertetning foretas ofte med varmt resp. kokende vann og betegnes som "sealing". Herved lukkes porene og dermed økes betraktelig korrosjonsbeskyttelsen. However, these anodically applied oxide layers do not meet all requirements with regard to corrosion protection as they have a porous structure. For this reason, it is necessary to seal the oxide layers. This sealing is often done with hot or boiling water and is referred to as "sealing". This closes the pores and thus significantly increases corrosion protection.
Ved ettertetning av anodisk påførte oksydsjikt lukkes imidlertid ikke bare porene, men det danner seg også på den samlede overflate et mer eller mindre sterkt silkeaktig belegg, det såkalte sealing-belegg. Dette består av hydratisert aluminiumoksyd og er ikke gripefast således at sjiktets dekorative effekt derved påvirkes. Videre nedsetter det klebefastheten ved sammenklebing av slike alu-miniumdeler og befordrer ved den økede effektive overflate senere tilsmussing og korrosjon. Av disse grunner var det hittil nødvendig mekanisk eller på kjemisk måte å fjerne belegget for- hånden. When sealing an anodically applied oxide layer, however, not only the pores are closed, but a more or less strong silky coating, the so-called sealing coating, also forms on the overall surface. This consists of hydrated aluminum oxide and is not grippy so that the decorative effect of the layer is thereby affected. Furthermore, it reduces the adhesive strength when gluing together such aluminum parts and promotes later soiling and corrosion due to the increased effective surface. For these reasons, it was previously necessary to mechanically or chemically remove the coating by hand.
Det er allerede kjent fra tettet og med sealingbelegg beheftede overflater ved en mineralsyre-etterbehandling igjen å utløse dette belegg. Ved denne fremgangsmåte er det således nødvendig med ytterligere behandlingstrinn og den krever dessuten en meget omhyggelig etterbehandling med mineralsyre for å utelukke sjiktbe-skadigelser. Videre hører det til teknikkens stand for å hindre sealing-belegg å gjennomføre en ettertetning med oppløsninger som inneholder nikkelacetat og ligninsulfat. Uheldig ved denne arbeidsmåte er blant annet misfargningen av de dannede oksydsjikt under lys-påvirkning. Det er også allerede omtalt fremgangsmåter hvor det for å hindre sealing-belegg foregår en varmtvannstetning under tilsetning av bestemte polyakrylater eller bestemte dekstriner. Disse fremgangsmåter har vist seg godt egnet. I mange tilfeller, spesielt ved ikke omhyggelig arbeidsmåte, kan det imidlertid bli tilbake opp-tørkningsrester. Disse er uønsket» De lar seg imidlertid lett fjerne ved en etterspyling. It is already known from sealed and sealed surfaces affected by a mineral acid finishing treatment to trigger this coating again. With this method, further treatment steps are thus necessary and it also requires a very careful post-treatment with mineral acid to exclude layer damage. Furthermore, it is part of the state of the art to prevent sealing coatings from carrying out resealing with solutions containing nickel acetate and lignin sulphate. Unfortunate with this method of working is, among other things, the discolouration of the formed oxide layers under the influence of light. Methods have also already been discussed where, in order to prevent sealing coatings, a hot water seal is carried out with the addition of specific polyacrylates or specific dextrins. These methods have proven to be well suited. However, in many cases, especially if the work is not done carefully, drying residues may remain. These are unwanted" They can, however, be easily removed by rinsing.
Det er nå blitt funnet at man kan forbedre ytterligere de hittil kjente arbeidsmåter når man betjener seg av nedenfor om-talte fremgangsmåte til behandling av overflater av aluminium eller aluminiumlegeringer ved anodisk oksydasjon med en etterfølgende tetning i vandig oppløsning ved forhøyede temperaturer. Fremgangsmåten ifølge oppfinnelsen er karakterisert ved at tetningen gjennom-føres ved temperaturer mellom 90°C og koketemperaturen og en pH-verdi fra 5 til 6,5 med oppløsninger som inneholder en eller flere It has now been found that the previously known working methods can be further improved when using the below-mentioned method for treating surfaces of aluminum or aluminum alloys by anodic oxidation with a subsequent seal in aqueous solution at elevated temperatures. The method according to the invention is characterized in that the sealing is carried out at temperatures between 90°C and the boiling temperature and a pH value from 5 to 6.5 with solutions containing one or more
. vannoppløselige med 2-verdige metaller kompleksdannende fosfonsyrer resp. deres vannoppløselige salter i en mengde av 0,001 - 0,05 g/liter, samt kalsiumioner, hvor det molare forhold kalsiumion : fosfonsyre minst utgjør 2:1. Det er kjent et større antall fosfonsyrer som danner komplekser med 2-verdige metaller. Fortrinnsvis anvendes forbindelser som tilsvarer de generelle formler, . water-soluble with divalent metals complex-forming phosphonic acids resp. their water-soluble salts in an amount of 0.001 - 0.05 g/litre, as well as calcium ions, where the molar ratio calcium ion : phosphonic acid is at least 2:1. A larger number of phosphonic acids are known which form complexes with divalent metals. Preferably, compounds corresponding to the general formulas are used,
R-^, R2 = et hydrogenatom eller en alkylrest med 1 til 4 C-atomer R-j = et hydrogenatom eller en alkylrest med 1 til 4 C-atomer R-^, R2 = a hydrogen atom or an alkyl radical with 1 to 4 carbon atoms R-j = a hydrogen atom or an alkyl radical with 1 to 4 carbon atoms
eller fenylrest or phenyl residue
X og Y = et hydrogenatom eller en alkylrest med 1 til 4 C-atomer Rjj = en -PO^R^-gruppe eller en gruppe med formelen X and Y = a hydrogen atom or an alkyl radical with 1 to 4 carbon atoms Rjj = a -PO^R^ group or a group of the formula
R'cj = et hydrogenatom, en metylgruppe eller en -CH2-CH2-COOH-gruppe. R'cj = a hydrogen atom, a methyl group or a -CH 2 -CH 2 -COOH group.
Som hydroksyalkandifosfonsyrer" med formel I kan det eksempelvis anvendes 1-hydroksypropan-, 1-hydroksybutan-, 1-hydroksy-pentan-, 1-hydroksyheksan-l,1-difosfonsyre samt 1-hydroksy-l-feny1-metan-1,1-difosfonsyre og fortrinnsvis 1-hydroksyetan-l,1-difosfon-syre. Som fosfonsyre med den generelle formel II kommer det f.eks. As hydroxyalkanediphosphonic acids" with formula I, 1-hydroxypropane-, 1-hydroxybutane-, 1-hydroxy-pentane-, 1-hydroxyhexane-1,1-diphosphonic acid and 1-hydroxy-1-phenyl-1-methane-1,1 can be used, for example -diphosphonic acid and preferably 1-hydroxyethane-1,1-diphosphonic acid As phosphonic acid with the general formula II there are e.g.
i betraktning: 1-aminoetan-, 1-amino-l-fenylmetan-, dimetylamino-etan-, dimetylaminobutan-, dietylaminometan-, propyl- og butylamino-metan-1,1-fosfonsyre. Eksempler for fosfonsyre med den generelle formel III er aminotrimetylenfosfonsyre, etylendiamintetrametylenfosfonsyre, dietylentriaminpentametylenfosfonsyre, aminotri- (2-propylen-2-fosfonsyre). Som fosfonsyre med den generelle formel IV kan det anvendes fosfonravsyre-l-fosfono-l-metylravsyre og 2-fosfonbutan-l,2, 4-trikarboksylsyre. in consideration: 1-aminoethane-, 1-amino-1-phenylmethane-, dimethylamino-ethane-, dimethylaminobutane-, diethylaminomethane-, propyl- and butylamino-methane-1,1-phosphonic acid. Examples of phosphonic acid with the general formula III are aminotrimethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, aminotri-(2-propylene-2-phosphonic acid). As phosphonic acid with the general formula IV, phosphosuccinic acid-1-phosphono-1-methylsuccinic acid and 2-phosphonobutane-1,2,4-tricarboxylic acid can be used.
Istedenfor de oppførte fosfonsyrer kan det også anvendes deres vannoppløselige salter som spesielt natrium-, kalium-, ammonium-, alkanolaminsalter. Fosfonsyrene eller deres vannoppløselige salter anvendes fortrinnsvis i en mengde fra 0,001 til 0,05 g/liter. De kan anvendes"enkeltvis eller i blanding. Spesielt har det hertil vist seg egnet en blanding av 1-hydroksyetan-l,1-disfosfonsyre og aminotrimetylenfosfonsyre i vektforhold fra 4:1 til 1:4. Instead of the listed phosphonic acids, their water-soluble salts can also be used, such as sodium, potassium, ammonium, alkanolamine salts in particular. The phosphonic acids or their water-soluble salts are preferably used in an amount of from 0.001 to 0.05 g/litre. They can be used individually or in a mixture. In particular, a mixture of 1-hydroxyethane-1,1-disphosphonic acid and aminotrimethylenephosphonic acid in a weight ratio of 4:1 to 1:4 has proven suitable for this purpose.
Fosfonsyrene resp» deres saltholdige oppløsninger inn-stilles hvis nødvendig til en pH-verdi fra 5 til 6,5. Denne innstilling kan foregå med ammoniakk resp. eddiksyre. If necessary, the phosphonic acids or their saline solutions are adjusted to a pH value of 5 to 6.5. This setting can be done with ammonia or acetic acid.
For fremstilling av oppløsningene kan det anvendes normalt vann som verken er helavsaltet eller mykgjort. Når det anvendes helavsaltet resp. destillert eller meget mykt vann til dannelse av oppløsningene, er det nødvendig med en tilsetning av kalsiumioner. Fortrinnsvis kan det anvendes vannoppløselig kalsiumsalter som CaC^ eller CaCNO^^. Molforholdet kalsiumioner: fosfonsyrer skal minst utgjøre 2:1. Vanligvis er det fordelaktig å anvende et høyere forhold kalsiumioner:fosfonsyrer fra ca. 5:1 til ca. 500:1. For the preparation of the solutions, normal water that is neither completely desalinated nor softened can be used. When fully desalted or distilled or very soft water to form the solutions, an addition of calcium ions is necessary. Preferably, water-soluble calcium salts such as CaC^ or CaCNO^^ can be used. The molar ratio of calcium ions: phosphonic acids must be at least 2:1. Generally, it is advantageous to use a higher ratio of calcium ions:phosphonic acids from about 5:1 to approx. 500:1.
En foretrukket utførelsesform av fremgangsmåten består A preferred embodiment of the method consists of
i at det til tetningsoppløsningen i tillegg settes et dekstrin i en mengde fra 0,1 til 5 g/liter, fortrinnsvis 0,1 til 2 g/liter. Det anvendes hertil spesielt dekstriner med en viskositet fra 50 til 400 cP i 50%- ig oppløsning ved 20°C, Viskositeten er herved målt med et Brookfield-rotasjonsviskosimeter. in that a dextrin is additionally added to the sealing solution in an amount of from 0.1 to 5 g/litre, preferably 0.1 to 2 g/litre. In particular, dextrins with a viscosity of 50 to 400 cP in a 50% solution at 20°C are used for this purpose. The viscosity is measured with a Brookfield rotary viscometer.
Ved fremgangsmåten ifølge oppfinnelsen er det mulig å hindre dannelsen av sealing-belegg uten at det anocH " V. z oksydsjikt påvirkes. Vanskeligheter ved hårdhetsdannere av vann opptrer ikke således at det også kan anvendes ikke avsaltet eller ikke mykgjort vann. Utfellinger av vannets hårdhetsdannere unngås sterkt eller ved vann av høy hårdhet danner det seg bare fnokket tunge utfellinger som ikke avsetter seg på ettertettede deler, men på bunnen og lett kan utspyles fra badene. Overflatens utseende påvirkes ikke ved fremgangsmåten ifølge oppfinnelsen. Det bibeholdes de effekter slik det ble oppnådd ved forbehandling og anodisering. Det er bare nød-vendig med meget små tilsetningsmengder ved fremgangsmåten ifølge oppfinnelsen. With the method according to the invention, it is possible to prevent the formation of a sealing coating without the anocH " V. z oxide layer being affected. Difficulties with water hardness formers do not occur such that non-desalinated or unsoftened water can also be used. Precipitation of the water hardness formers is avoided strongly or with water of high hardness, only very heavy deposits form which do not settle on sealed parts, but on the bottom and can be easily washed out of the baths. The appearance of the surface is not affected by the method according to the invention. The effects as achieved by pre-treatment and anodizing Only very small amounts of addition are necessary in the method according to the invention.
I de følgende eksempler foregår betegnelsen av aluminium-legeringene ifølge DIN 1725. Oksydsjiktets kvalitet ble bestemt ved den såkalte tilsynelatende ledeverdi ifølge DIN 50 949 og ved taps-faktoren d ifølge DIN-utkastet 50920, In the following examples, the designation of the aluminum alloys takes place according to DIN 1725. The quality of the oxide layer was determined by the so-called apparent conductivity value according to DIN 50 949 and by the loss factor d according to the DIN draft 50920,
Eksempel 1. Example 1.
På vanlig måte a-kalisk avfettede og beisede aluminium-profiler (AlMg 3)» som var oksydert anodisk ved likestrøm-svovelsyre-fremgangsmåten (sjikttykkelse 22^,um) , ble tettet ved 100°C i 70 minutter, med en oppløsning av 0,003 g/liter 1-hydroksyetan-l,1-difos-fonsyre og 0,5 g/liter dekstrin (viskositet 100 cP, målt i 50%- ig oppløsning ved 20°C) i vann av 15°dH, som med ammoniakk var innstilt på en pH-verdi på 5j8. Profilene viste intet sealing-belegg, sjikt-tykkelsen var uforandret og tilsynelatende ledeverdi (y = 8,5) og tapsfaktor (d = 0,41) viste en god tetning. Heller ikke etter lengre bruk viste det seg i tetningsoppløsningene faste utfellinger av vann-hårdhetsdannere. Det dannet seg et fnokket, tungt bunnbelegg som ikke avsatte seg på profilene og som lett kunne fjernes ved ut-sprøytning fra badet. Det samme resultat ble oppnådd når det istedenfor 1-hydroksyetan-ljl-difosfonsyre ble anvendt en di-, tri- In the usual way, alkali-degreased and stained aluminum profiles (AlMg 3 ), which had been oxidized anodically by the direct current sulfuric acid method (layer thickness 22 µm), were sealed at 100°C for 70 minutes, with a resolution of 0.003 g/litre 1-hydroxyethane-1,1-diphosphonic acid and 0.5 g/litre dextrin (viscosity 100 cP, measured in 50% solution at 20°C) in water of 15°dH, which with ammonia was adjusted to a pH value of 5j8. The profiles showed no sealing coating, the layer thickness was unchanged and the apparent conductivity value (y = 8.5) and loss factor (d = 0.41) showed a good seal. Even after prolonged use, solid deposits of water-hardness formers did not appear in the sealing solutions. A dirty, heavy bottom coating formed which did not settle on the profiles and which could easily be removed by spraying out from the bathroom. The same result was obtained when, instead of 1-hydroxyethane-ljl-diphosphonic acid, a di-, tri-
og tetranatrium- resp. kalium-, eller ammoniumsalter eller et tri-etanolaminsalt. pH-innstillingen ble ved de alkaliske salter gjennom-ført med eddiksyre. and tetrasodium resp. potassium or ammonium salts or a tri-ethanolamine salt. For the alkaline salts, the pH was adjusted with acetic acid.
Eksempel 2. Example 2.
På vanlig måte avfettet aluminiumsblikk (AlSi 5),som var anodisk oksydert i likestrøm-svovelsyre-oksalsyre-fremgangsmåten (sjikttykkelse 21^um) ble tettet ved 100°C i 60 minutter med en opp-løsning av 0,007 g/liter 1-hydroksyetan-l,1-difosfonsyre i avionisert vann under tilsetning av 10 mg/liter kalsiumioner og innstilling av pH.på 5,6 med ammoniakk. Conventionally degreased aluminum tin (AlSi 5 ), which was anodically oxidized in the direct current sulfuric acid-oxalic acid process (layer thickness 21 µm) was sealed at 100°C for 60 minutes with a solution of 0.007 g/liter 1-hydroxyethane -1,1-diphosphonic acid in deionized water while adding 10 mg/litre calcium ions and adjusting the pH to 5.6 with ammonia.
Blikkene viste ingen sealing-belegg og tilsynelatende ledeverdi (y = 12) og tapsfaktor (d = 0,49) viste en god tetning. The glasses showed no sealing coating and apparent conductivity (y = 12) and loss factor (d = 0.49) showed a good seal.
De samme resultater kunne oppnås med di-, tri- og tetraalkali- resp. ammoniumsalter. The same results could be obtained with di-, tri- and tetraalkali resp. ammonium salts.
Eksempel 3. Example 3.
På vanlig måte alkalisk•avfettet og beiset aluminiumprofil (AlMgSiO,5) som var anodisk oksydert etter en autocolor-fremgangsmåte (sjikttykkelse l8^um), ble tettet ved 100°C i 60 minutter i en oppløsning av 0,005 g/liter 1-hydroksyetan-l,1-difosfon-syre og 0,005 g/liter aminotrimetylenfosfonsyre og 1 g/liter dekstrin (viskositet 200 cP, målt i 50%-ig oppløsning ved 20°C) i vann av 35° dH, innstilt med ammoniakk til en pH-verdi på 5,9. Profilene viste intet sealingbelegg og en god tetning ble angitt ved tilsynelatende ledeverdi (y = 10,5) og tapsfaktor (d = 0,47). Vannhårdheten gjorde seg herved ikke forstyrrende bemerkbar da den falt u i fnokket, lett avsettbar form. In the usual way alkaline•degreased and stained aluminum profile (AlMgSiO,5) which was anodically oxidized according to an autocolor method (layer thickness 18 µm) was sealed at 100°C for 60 minutes in a solution of 0.005 g/liter 1-hydroxyethane -1,1-diphosphonic acid and 0.005 g/liter aminotrimethylenephosphonic acid and 1 g/liter dextrin (viscosity 200 cP, measured in 50% solution at 20°C) in water of 35° dH, adjusted with ammonia to a pH -value of 5.9. The profiles showed no sealing coating and a good seal was indicated by apparent conductivity (y = 10.5) and loss factor (d = 0.47). The water hardness did not make itself disturbingly noticeable as it fell out in a neat, easily removable form.
Praktisk talt samme resultater ble oppnådd når det istedenfor ovennevnte fosfonsyrer ble anvendt deres alkali- eller ammoniumsalter, hvor de alkalisk reagerende salter ble innstilt med eddiksyre på en pH-verdi mellom 5,8 og 6,0. Practically the same results were obtained when, instead of the above-mentioned phosphonic acids, their alkali or ammonium salts were used, where the alkaline reacting salts were adjusted with acetic acid to a pH value between 5.8 and 6.0.
Eksempel 4. Example 4.
Aluminiumprofil (AlMgSiO, 5), som på vanlig måte var alkalisk avfettet og beiset, ble oksydert anodisk i likestrøm-svovelsyre-fremgangsmåten (sjikttykkelse 20 til 22^,um). Profilene ble fortettet i -en oppløsning som inneholdt 0,01 g/liter 1-hydroksy-etan-l ,1-difosf onsyre og 2 g/liter dekstrin (viskositet 150 cP, målt i 50%- ig oppløsning ved 20°C) tettet ved 98 - 100°C ved 60 minutter i vann av 20° dH, innstilt med ammoniakk til en pH-verdi på 5,8. Profilene viste intet sealing-belegg, tilsynelatende ledeverdi Aluminum profile (AlMgSiO, 5), which was conventionally alkaline degreased and stained, was oxidized anodically in the direct current sulfuric acid process (layer thickness 20 to 22 µm). The profiles were condensed in a solution containing 0.01 g/liter 1-hydroxy-ethane-1,1-diphosphonic acid and 2 g/liter dextrin (viscosity 150 cP, measured in a 50% solution at 20°C) sealed at 98 - 100°C for 60 minutes in water of 20° dH, adjusted with ammonia to a pH value of 5.8. The profiles showed no sealing coating, apparently conductive value
(y = 9,0) og tapsfaktor (d = 0,40) viste en god tetning. Forstyrrelser ved vannets hårdhetsdannere opptrådte ikke. (y = 9.0) and loss factor (d = 0.40) showed a good seal. Disturbances at the water hardness generators did not occur.
Eksempel 5. Example 5.
På samme måte som omtalt i eksempel 4, ble aluminium-profiler tettet i oppløsninger som istedenfor 1-hydroksyetan-l,1-difosfonsyre inneholdt en av de følgende oppførte fosfonsyrer i samme mengde: 1-hydroksypropan-1,1-difosfonsyre In the same way as discussed in example 4, aluminum profiles were sealed in solutions which instead of 1-hydroxyethane-1,1-diphosphonic acid contained one of the following listed phosphonic acids in the same amount: 1-hydroxypropane-1,1-diphosphonic acid
1-hydroksyheksan-l,1-disfosfonsyre 1-Hydroxyhexane-1,1-disphosphonic acid
1- aminoetan-l,1-difosfonsyre 1-aminoethane-1,1-diphosphonic acid
dimetylaminometan-1,1-difosfonsyre dimethylaminomethane-1,1-diphosphonic acid
etylendiamintetrametylenfosfonsyre ethylenediaminetetramethylenephosphonic acid
2- fosfonobutan-1,2,4-trikarboksylsyre 1-fosfono-l-metylravsyre.■ 2-phosphonobutane-1,2,4-tricarboxylic acid 1-phosphono-1-methylsuccinic acid.■
I alle tilfeller opptrådte intet sealing-belegg. Det ble ikke iakttatt noen forstyrrelser på grunn av vannets hårdhet og tilsynelatende ledningsverdi (y = 10 til 12) og tapsfaktor (d = In all cases, no sealing coating occurred. No disturbances were observed due to the hardness of the water and apparent conductivity value (y = 10 to 12) and loss factor (d =
0,43 til 0,52) viste en god tetning. 0.43 to 0.52) showed a good seal.
Samme resultater ble oppnådd når det istedenfor de ovennevnte fosfonsyrer ble anvendt deres alkali- resp. ammoniumsalter i ekvivalente mengder. The same results were obtained when, instead of the above-mentioned phosphonic acids, their alkali resp. ammonium salts in equivalent quantities.
Claims (6)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2211553A DE2211553C3 (en) | 1972-03-10 | 1972-03-10 | Process for compacting anodic oxide layers on aluminum and aluminum alloys |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| NO131208B true NO131208B (en) | 1975-01-13 |
| NO131208C NO131208C (en) | 1975-04-23 |
Family
ID=5838488
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO693/73A NO131208C (en) | 1972-03-10 | 1973-02-20 |
Country Status (17)
| Country | Link |
|---|---|
| US (1) | US3900370A (en) |
| JP (1) | JPS565835B2 (en) |
| AT (1) | AT317627B (en) |
| BE (1) | BE796534A (en) |
| BR (1) | BR7301707D0 (en) |
| CA (1) | CA1005788A (en) |
| CH (1) | CH578053A5 (en) |
| DE (1) | DE2211553C3 (en) |
| DK (1) | DK150715C (en) |
| ES (1) | ES412477A1 (en) |
| FR (1) | FR2175808B1 (en) |
| GB (1) | GB1419597A (en) |
| IT (1) | IT982499B (en) |
| NL (1) | NL171914C (en) |
| NO (1) | NO131208C (en) |
| SE (1) | SE383764B (en) |
| ZA (1) | ZA731678B (en) |
Families Citing this family (32)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4116695A (en) * | 1974-09-12 | 1978-09-26 | Fuji Photo Film Co., Ltd. | Method of producing a support for a printing plate |
| GB1527124A (en) * | 1975-03-07 | 1978-10-04 | Emi Ltd | Modulated groove records |
| US4202706A (en) * | 1979-03-12 | 1980-05-13 | Minnesota Mining And Manufacturing Company | Corrosion resistance treatment of aluminum with N-alkyl-fluoroaliphaticsulfonamidophosphonic acids and salts thereof |
| US4320023A (en) * | 1979-08-23 | 1982-03-16 | Conoco Inc. | Antifreeze formulation useful for retarding precipitation of aluminum corrosion products in the cooling systems of internal combustion engines |
| DE3006094A1 (en) * | 1980-02-19 | 1981-08-20 | Hoechst Ag, 6000 Frankfurt | METHOD FOR PRESERVATING FLAT PRINTING FORMS |
| US4308079A (en) * | 1980-06-16 | 1981-12-29 | Martin Marietta Corporation | Durability of adhesively bonded aluminum structures and method for inhibiting the conversion of aluminum oxide to aluminum hydroxide |
| DE3126626A1 (en) | 1981-07-06 | 1983-01-20 | Hoechst Ag, 6000 Frankfurt | HYDROPHILIZED CARRIER MATERIALS FOR OFFSET PRINTING PLATES, A METHOD FOR THEIR PRODUCTION AND THEIR USE |
| DE3126636A1 (en) | 1981-07-06 | 1983-01-27 | Hoechst Ag, 6000 Frankfurt | HYDROPHILIZED CARRIER MATERIALS FOR OFFSET PRINTING PLATES, A METHOD FOR THEIR PRODUCTION AND THEIR USE |
| US4381226A (en) * | 1981-12-23 | 1983-04-26 | American Hoechst Corporation | Electrochemical treatment of aluminum in non-aqueous polymeric polybasic organic acid containing electrolytes |
| US4388156A (en) * | 1981-12-23 | 1983-06-14 | American Hoechst Corporation | Aluminum electrolysis in non-aqueous monomeric organic acid |
| US4427459A (en) | 1982-01-25 | 1984-01-24 | Pennwalt Corporation | Phosphate conversion coatings for metals with reduced coating weights and crystal sizes |
| US4526671A (en) * | 1982-09-24 | 1985-07-02 | Pilot Man-Nen-Hitsu Kabushiki Kaisha | Surface treatment of aluminum or aluminum alloys |
| GB8309571D0 (en) * | 1983-04-08 | 1983-05-11 | Albright & Wilson | Accelerated sealing of anodised aluminium |
| CS253788B1 (en) * | 1985-08-13 | 1987-12-17 | Ivan Emmer | Method for electric moisture-content sensor production |
| JPH078389B2 (en) * | 1985-10-07 | 1995-02-01 | 三菱アルミニウム株式会社 | Method for manufacturing heat exchanger member |
| US4778533A (en) * | 1987-02-04 | 1988-10-18 | Aluminum Company Of America | Aluminum-magnesium alloy sheet product and method for inhibiting formation of a film thereon |
| US4781984A (en) * | 1987-04-28 | 1988-11-01 | The Dow Chemical Company | Aromatic polyether resins having improved adhesion |
| US4777091A (en) * | 1987-04-28 | 1988-10-11 | The Dow Chemical Company | Metal substrates treated with aminophosphonic acid compounds and products resulting from coating such substrates |
| IT1210727B (en) * | 1987-05-12 | 1989-09-20 | Gevipi Ag | PROCEDURE FOR THE PRODUCTION OF HARD SURFACE CONTROL BODIES FOR TAPS AND PRODUCTS THAT RESULT |
| DE3820650A1 (en) * | 1988-06-18 | 1989-12-21 | Henkel Kgaa | METHOD FOR COMPRESSING ANODIZED OXIDE LAYERS ON ALUMINUM AND ALUMINUM ALLOYS |
| US5103550A (en) * | 1989-12-26 | 1992-04-14 | Aluminum Company Of America | Method of making a food or beverage container |
| JP2648976B2 (en) * | 1990-03-09 | 1997-09-03 | 富士写真フイルム株式会社 | Photosensitive lithographic printing plate |
| DE4039920A1 (en) * | 1990-12-14 | 1992-06-17 | Basf Ag | NEW POLYETHYLENIMINE AND POLYVINYLAMINE DERIVATIVES, CARRIER MATERIALS COATED WITH THESE DERIVATIVES ON THE BASIS OF ALUMINUM AND THE USE THEREOF FOR THE PRODUCTION OF OFFSET PRINTING PLATES |
| US5178916A (en) * | 1991-06-21 | 1993-01-12 | At&T Bell Laboratories | Process for making corrosion-resistant articles |
| US5736256A (en) * | 1995-05-31 | 1998-04-07 | Howard A. Fromson | Lithographic printing plate treated with organo-phosphonic acid chelating compounds and processes relating thereto |
| US5622569A (en) * | 1995-06-02 | 1997-04-22 | Aluminum Company Of America | Aluminum rigid container sheet cleaner and cleaning method |
| ES2142619T3 (en) * | 1995-10-18 | 2000-04-16 | Henkel Kgaa | HOT SEALING OF SHORT DURATION OF ANODIZED METALLIC SURFACES. |
| WO1997018905A1 (en) * | 1995-11-20 | 1997-05-29 | Berg Technology, Inc. | Method of providing corrosion protection |
| DE19621818A1 (en) * | 1996-05-31 | 1997-12-04 | Henkel Kgaa | Short-term hot compression of anodized metal surfaces with solutions containing surfactants |
| WO2003016596A1 (en) * | 2001-08-14 | 2003-02-27 | Magnesium Technology Limited | Magnesium anodisation system and methods |
| JP2003194662A (en) * | 2001-12-27 | 2003-07-09 | Nihon Tetra Pak Kk | Sealing state inspection device |
| US10138566B2 (en) * | 2017-01-13 | 2018-11-27 | Macdermid Acumen, Inc. | Sealing anodized aluminum using a low-temperature nickel-free process |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3012917A (en) * | 1957-03-26 | 1961-12-12 | Pechiney Prod Chimiques Sa | Method of protecting metal surfaces |
| BE606888A (en) * | 1960-08-05 | 1900-01-01 | ||
| NL274316A (en) * | 1961-02-08 | |||
| US3630790A (en) * | 1969-05-13 | 1971-12-28 | Dow Chemical Co | Method of protection of metal surfaces from corrosion |
| BE755573A (en) * | 1969-09-02 | 1971-03-01 | Henkel & Cie Gmbh | PROCESS FOR TREATING ALUMINUM SURFACES AND ALUMINIU ALLOYS |
| US3634146A (en) * | 1969-09-04 | 1972-01-11 | American Cyanamid Co | Chemical treatment of metal |
| JPS498775B1 (en) * | 1970-05-13 | 1974-02-28 |
-
1972
- 1972-03-10 DE DE2211553A patent/DE2211553C3/en not_active Expired
-
1973
- 1973-02-20 DK DK089173A patent/DK150715C/en not_active IP Right Cessation
- 1973-02-20 NO NO693/73A patent/NO131208C/no unknown
- 1973-02-20 SE SE7302384A patent/SE383764B/en unknown
- 1973-02-23 US US335065A patent/US3900370A/en not_active Expired - Lifetime
- 1973-03-08 NL NLAANVRAGE7303294,A patent/NL171914C/en not_active IP Right Cessation
- 1973-03-08 FR FR7308272A patent/FR2175808B1/fr not_active Expired
- 1973-03-09 IT IT21387/73A patent/IT982499B/en active
- 1973-03-09 BR BR731707A patent/BR7301707D0/en unknown
- 1973-03-09 CH CH352373A patent/CH578053A5/xx not_active IP Right Cessation
- 1973-03-09 ZA ZA731678A patent/ZA731678B/en unknown
- 1973-03-09 CA CA165,719A patent/CA1005788A/en not_active Expired
- 1973-03-09 AT AT210573A patent/AT317627B/en not_active IP Right Cessation
- 1973-03-09 GB GB1146573A patent/GB1419597A/en not_active Expired
- 1973-03-09 ES ES412477A patent/ES412477A1/en not_active Expired
- 1973-03-09 BE BE128589A patent/BE796534A/en not_active IP Right Cessation
- 1973-03-10 JP JP2846673A patent/JPS565835B2/ja not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DK150715C (en) | 1987-12-28 |
| DE2211553B2 (en) | 1977-08-04 |
| BR7301707D0 (en) | 1974-06-27 |
| NL7303294A (en) | 1973-09-12 |
| FR2175808B1 (en) | 1976-04-09 |
| DE2211553A1 (en) | 1973-09-13 |
| FR2175808A1 (en) | 1973-10-26 |
| JPS48102751A (en) | 1973-12-24 |
| CH578053A5 (en) | 1976-07-30 |
| CA1005788A (en) | 1977-02-22 |
| NO131208C (en) | 1975-04-23 |
| NL171914C (en) | 1983-06-01 |
| BE796534A (en) | 1973-09-10 |
| NL171914B (en) | 1983-01-03 |
| DK150715B (en) | 1987-06-01 |
| GB1419597A (en) | 1975-12-31 |
| JPS565835B2 (en) | 1981-02-06 |
| AT317627B (en) | 1974-09-10 |
| DE2211553C3 (en) | 1978-04-20 |
| IT982499B (en) | 1974-10-21 |
| ES412477A1 (en) | 1976-05-16 |
| ZA731678B (en) | 1973-12-19 |
| US3900370A (en) | 1975-08-19 |
| SE383764B (en) | 1976-03-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| NO131208B (en) | ||
| RU2420615C2 (en) | Production item and procedure for anode application of coating out of oxide ceramics on aluminium and/or titanium | |
| US4148670A (en) | Coating solution for metal surface | |
| US4225398A (en) | Method of improving the corrosion resistance of an anodically oxidized surface film on aluminum articles | |
| US6280598B1 (en) | Anodization of magnesium and magnesium based alloys | |
| US5478415A (en) | Process and composition for sealing anodized aluminum surfaces | |
| US3876435A (en) | Chromate conversion coating solutions having chloride, sulfate, and nitrate anions | |
| JPH0577750B2 (en) | ||
| EP0575244B1 (en) | Process for treating aluminium-based substrates before their anodisation, bath used in this process and concentrate for preparing this bath | |
| US3838023A (en) | Sealing anodized aluminum | |
| US5374455A (en) | Process for sealing aluminum oxide films | |
| US4939001A (en) | Process for sealing anodized aluminum | |
| US5074972A (en) | Surface treatment of ti or ti alloy parts for enhancing adhesion to organic material | |
| US4678519A (en) | Method of zinc phosphatization, activation and refining bath used in said method and corresponding concentrate | |
| US4648911A (en) | Sealing process | |
| NO159945B (en) | PROCEDURE FOR THE CONTINUATION OF ANODICALLY MADE OUTSIDE LAYOUT OF ALUMINUM OR ALUMINUM ALLOYS. | |
| KR102077555B1 (en) | Coloured trivalent chromate corrosion-resistant enhancer agent for Zinc-Nickel plating and Surface treatment of Zinc-Nickel plating layer using the same | |
| US2472864A (en) | Composition for and method of chemically coating aluminum | |
| US4288299A (en) | Enhanced hydrothermal sealing of anodized aluminum | |
| GB1590597A (en) | Treating a1 or a1 alloy surfaces | |
| NO803937L (en) | PROCEDURE AND SOLUTION FOR COATING ALUMINUM | |
| JP3987326B2 (en) | Sealing method for anodized film of aluminum or aluminum alloy | |
| US5259937A (en) | Process for forming colorless chromate coating film on bright aluminum wheel | |
| US6506263B1 (en) | Sealant composition | |
| US2146838A (en) | Method of coating aluminum |