DK150715B - PROCEDURE FOR SEALING ANODICALLY GENERATED OXIDE LAYERS ON ALUMINUM OR ALUMINUM ALLOYS - Google Patents
PROCEDURE FOR SEALING ANODICALLY GENERATED OXIDE LAYERS ON ALUMINUM OR ALUMINUM ALLOYS Download PDFInfo
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- DK150715B DK150715B DK089173AA DK89173A DK150715B DK 150715 B DK150715 B DK 150715B DK 089173A A DK089173A A DK 089173AA DK 89173 A DK89173 A DK 89173A DK 150715 B DK150715 B DK 150715B
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- 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
150715 f150715 f
Opfindelsen angår en fremgangsmåde til tætning af anodisk frembragte oxidlag på aluminium eller aluminiumlegeringer i vandige opløsninger indeholdende phosphonsyrer eller deres salte og calciumioner med en pH-værdi på 5 til 6,5 ved temperaturer mellem 90°C og kogepunktet.The invention relates to a method for sealing anodically generated oxide layers on aluminum or aluminum alloys in aqueous solutions containing phosphonic acids or their salts and calcium ions having a pH of 5 to 6.5 at temperatures between 90 ° C and the boiling point.
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Ved fremgangsmåden forhindres dannelse af forstyrrende aluminiumhy-droxidbelægninger (sealingbelægninger) på overfladerne og undgås vanskeligheder på grund af vandets hårdhedssalte.The process prevents the formation of disruptive aluminum hydroxide coatings (sealing coatings) on the surfaces and avoids difficulties due to the water hardness salts.
Med henblik på korrosionsbeskyttelse påføres der på aluminiumoverflader ofte anodisk frembragte oxidlag. Disse oxidlag beskytter aluminium overfladerne mod vejrligets påvirkninger og andre korroderende medier.For the purpose of corrosion protection, anodic oxide layers are often applied to aluminum surfaces. These oxide layers protect the aluminum surfaces from the effects of weather and other corrosive media.
' Endvidere påføres de anodiske oxidlag også for at få hårdere overflade og dermed opnå en større slidstyrke af aluminiummet. På grund af oxid-15 lagenes egenfarve eller deres delvis lette farvelighed kan der opnås særligt dekorative virkninger.Furthermore, the anodic oxide layers are also applied to obtain a harder surface and thus achieve a greater wear resistance of the aluminum. Due to the intrinsic color or partial lightness of the oxide layers, particularly decorative effects can be obtained.
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Til påføring af anodiske oxidlag på aluminium kendes en række fremgangsmåder. F.eks. sker frembringelse af oxidlag med jævnstrøm i opløsninger af svovlsyre (jævnstrøm-svovlsyre-metode). Ofte anvendes dog også opløsninger af organiske syrer, især sulfophthalsyre eller 5 sulfanilsyre eller disse i blanding med svovlsyre. De sidstnævnte fremgangsmåder er især kendt som autocolor-metoder.A number of methods are known for applying anodic oxide layers to aluminum. Eg. For example, DC oxide layers are produced in solutions of sulfuric acid (DC-sulfuric acid method). However, often solutions of organic acids, especially sulfophthalic acid or sulphanilic acid, or these in admixture with sulfuric acid are also used. The latter methods are especially known as autocolor methods.
Disse anodisk påførte oxidlag opfylder imidlertid ikke alle krav med henblik på korrosionsbeskyttelse, da de har en porøs struktur. Af 10 denne grund er det nødvendigt bagefter at tætne oxidlagene. Denne eftertætning foretages ofte med varmt eller kogende vand og betegnes "sealing”. Herved lukkes porerne, og korrosionsbeskyttelsen forøges dermed betydeligt.However, these anodically applied oxide layers do not meet all the requirements for corrosion protection as they have a porous structure. For this reason, it is necessary afterwards to seal the oxide layers. This sealing is often done with hot or boiling water and is termed “sealing.” This closes the pores, thus greatly increasing the corrosion protection.
15 Ved eftertætning af anodisk påførte oxidlag bliver imidlertid ikke kun porerne lukket, men der danner sig også på hele fladen en mere eller mindre tyk fløjlsagtig belægning, den såkaldte sealingbelægning Denne består af hydratiseret aluminiumoxid og er ikke gribefast, således at den dekorative virkning af laget derved skades. Endvidere 20 formindsker den hæfteevnen ved klæbning af sådanne aluminiumdele og fremmer senere tilsmudsning og korrosion som følge af den forstørrede effektive overflade. Af disse grund har det hidtil været nødvendigt at fjerne belægningen mekanisk med hånden eller ad kemisk vej.However, when sealing anodically applied oxide layers, not only are the pores closed, but also a more or less thick velvety coating is formed on the entire surface, the so-called sealing coating. This consists of hydrated alumina and is non-gripping, so that the decorative effect of the layer thereby being damaged. Furthermore, it decreases the adhesiveness of adhering such aluminum parts and later promotes soiling and corrosion due to the enlarged effective surface. For this reason, it has so far been necessary to remove the coating mechanically by hand or by chemical means.
25 Det er allerede kendt at fjerne denne belægning igen fra tætnede og med sealingbelægning behæftede overflader ved hjælp af en mineralsyre· efterbehandling. Ved denne fremgangsmåde er et yderligere behandlingstrin således nødvendigt, og den kræver desuden en meget omhyggelig efterbehandling med mineralsyren for at udelukke en .beskadigelse af 30 laget. Det hører endvidere til teknikkens standpunkt med henblik på forhindring af sealingbelægninger at udføre en eftertætning med opløsninger, som indeholder nikkelacetat og ligninsulfat. En ulempe ved denne arbejdsmåde er det bl.a., at de fremkomne oxidlag gulner under indflydelse af lyset. Der er også beskrevet fremgangsmåder, ved 35 hvilke der til forhindring af sealingbelægninger sker en varmtvands-tætning under tilsætning af bestemte polyacrylater eller bestemte dextriner. Disse fremgangsmåder har vist sig udmærkede. I mange tilfælde, især når der ikke arbejdes omhyggeligt, kan der dog blive tørringsrester tilbage. Disse er uønskede. De kan dog let fjernes 40 ved en efterskylning.25 It is already known to remove this coating again from sealed and sealing coating surfaces using a mineral acid · finishing. Thus, in this process, an additional treatment step is necessary and, in addition, it requires a very careful post-treatment with the mineral acid to exclude damage to the layer. It is also a matter of the prior art to prevent sealing coatings from performing a sealing with solutions containing nickel acetate and lignin sulfate. One disadvantage of this way of working is that the resulting oxide layers yellowish under the influence of light. Methods have also been described in which to prevent sealing coatings, a hot water seal occurs during the addition of certain polyacrylates or certain dextrins. These methods have proved excellent. However, in many cases, especially when not working carefully, drying residue may remain. These are undesirable. However, they can easily be removed by a rinsing.
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Fra DE - fremlæggelsesskrift nr. 1175524 kendes en fremgangsmåde €11 behandling af overfladen af aluminium ved anodisk frembringelse af oxidlag med en påfølgende tætning i en vandig opløsning ved en temperatur mellem 90°C og kogepunktet og med en PH-værdi på 5 5-6,5, idet opløsningen kan indeholde phosphonsyrer eller deres salte, herunder af calcium. Opløsningerne indeholder organiske forbindelser med mindst tre elektronegative grupper i molekylet, derunder mindst en fri eller en med en uorganisk eller organisk base mættet syregruppe. Syregrupperne kan også være phosphonsyregrupper. Som 10 eksempel nævnes polyfluoralkylphosphonsyre. I stedet for syrerne kan også anvendes de vandopløselige salte, blandt hvilke der bl. a. nævnes calciumsalte. Ved denne fremgangsmåde drejer det sig om at tilvejebringe overtræk, hvilket netop skal undgås ved fremgangsmåden ifølge den foreliggende opfindelse, samt opnå en tætning. End-15 videre berøres problemet om forhindring af sealingbelægninger ikke.From DE-Specification No. 1175524 a method is known for € 11 treatment of the surface of aluminum by anodic generation of oxide layers with a subsequent seal in an aqueous solution at a temperature between 90 ° C and the boiling point and having a pH of 5 5-6 The solution may contain phosphonic acids or their salts, including calcium. The solutions contain organic compounds with at least three electronegative groups in the molecule, including at least one free or one with an inorganic or organic base saturated acid group. The acid groups may also be phosphonic acid groups. As an example, polyfluoroalkylphosphonic acid is mentioned. Instead of the acids, the water-soluble salts, among which, e.g. a. Mention calcium salts. This method is to provide coatings which are precisely to be avoided by the method of the present invention and to obtain a seal. Furthermore, the problem of preventing sealing coatings is not affected.
Formålet med den foreliggende opfindelse er at angive en fremgangsmåde, som undgår de førnævnte ulemper, og som derfor gør det muligt at forhindre dannelsen af sealingbelægninger, og som undgår vanske-20 ligheder som følge af vandets hårdhedsdannere, således at der også kan anvendes ikke-afsaltet eller ikke-afhærdet vand. Udfældninger af vandets hårdhedsdannere undgås vidtgående, eller med vand af stor hårdhed dannes kun fnuggede, tunge bundfald, der ikke afsætter sig på de eftertætnede dele, men på bunden og let kan skylles ud 25 af badene. Overfladens udseende påvirkes ikke af fremgangsmåden ifølge opfindelsen, men der bibeholdes de virkninger, som opnås ved forbehandlingen og anodiseringen.The object of the present invention is to provide a method which avoids the aforementioned disadvantages and which therefore makes it possible to prevent the formation of sealing coatings and which avoids difficulties due to the hardness of the water, so that non-sealing agents can also be used. desalinated or uncured water. Precipitations of the hardness of the water are avoided far, or with water of great hardness only fluffy, heavy precipitates are formed, which do not settle on the sealed parts, but on the bottom and can easily be rinsed out of the baths. The appearance of the surface is not affected by the method according to the invention, but the effects obtained by the pretreatment and anodization are retained.
Fremgangsmåde ifølge opfindelsen er ejendommelig ved, at man udfører 30 tætningen med opløsninger, som indeholder en eller flere phosphonsyrer eller deres vandopløselige salte, som danner komplekser med divalente metaller, i en mængde på 0,001 til 0,05 g/1 samt calciumioner, idet det molære forhold mellem calciumioner op phosphonsyrer er mindst 2:1, hvilke phosphonsyrer har de almene formler 35 RThe process according to the invention is characterized in that the sealing is carried out with solutions containing one or more phosphonic acids or their water-soluble salts which form complexes with divalent metals in an amount of 0.001 to 0.05 g / l and calcium ions, molar ratios of calcium ions up phosphonic acids are at least 2: 1 which phosphonic acids have the general formulas 35 R
H2^3P " c ” p®3H2 (r = PhenYlrest eller alkylrest med 1 til 5 I C-atomer)H 2 ^ 3 P "c" p® 3 H 2 (r = Phenyl residue or alkyl residue having 1 to 5 I C atoms)
Fortrinsvis hydroxyethandiphosphonsyre, 4 150715Preferably hydroxyethanediphosphonic acid, 4 150715
^>N - C<^" II^> N - C <^ "II
R;T ^^·Ρ03Η2 hvor og R2 er et hydrogenatom eller alkylrest med 1 til 4 C-atomer R3 er et hydrogenatom eller alkylrest med 1 til 4 C-atomer eller phenylrest, r4 ' CXY\R 2 is a hydrogen atom or alkyl radical of 1 to 4 C atoms R 3 is a hydrogen atom or alkyl radical of 1 to 4 C atoms or phenyl radical, R 4 'CXY \
^;N - CXY - P03H2 III^; N - CXY - PO3H2 III
h2po3 - CXY^ hvor X og Y er et hydrogenatom eller en alkylrest med 1 til 4 C-atomei R^ er en -PO^I^-gruppe eller en gruppe af formlen CXY P0,Ho X 32 - CH2 - N eller cxy - po3h2 cxy - po3h2 -ch2-/ xcxyp3h2wherein X and Y are a hydrogen atom or an alkyl radical of 1 to 4 C atoms in R 2 is a -PO 1 group or a group of the formula CXY P0, Ho X 32 - CH 2 - N or cxy - po3h2 cxy - po3h2 -ch2- / xcxyp3h2
XCXY - CH2 - NXCXY - CH2 - N
CXYP03H2 eller R5CXYP03H2 or R5
I JI J
H203P - C - COOHH 2 O 3 P - C - COOH
H2 - C - COOH IVH2 - C - COOH IV
hvor Rg er et hydrogenatom, en methylgruppe eller en-CH2-CH2~COOH-gruppe 5 150715wherein R 9 is a hydrogen atom, a methyl group or a-CH 2 -CH 2 -COOH group 5
Som hydroxyalkandiphosphonsyre af formlen I kan der f.eks. anvendes 1-hydroxypropan-, 1-hydroxybutan-, 1-hydroxypentan-, 1-hydroxyhexan- 1,1-diphosphonsyre samt 1-hydroxy-l-phenylmethan-l,1-diphosphonsyre og fortrinsvis 1-hydroxyethan-l,1-diphosphonsyre. Som phosphonsyre 5 af den almene formel II kan der f.eks. være tale om: 1-aminoethan-, 1-amino-l-phenylmethan-, dimethylaminoethan-, dimethylaminobutan-, diethylaminomethan-, propyl- og butylaminomethan-1,1-diphosphonsyre. Eksempler på phosphonsyrer af den almene formel III er aminotrimethy enphosphonsyre, ethylendiamintetramethylenphosphonsyre, diethylen= 10 triaminpentamethylenphosphonsyre, aminotri- (2-propylen-2-phosphon= syre). Som phosphonsyrer af den almene formel IY kan der anvendes phosphonravsyre, 1-phosphon-l-methylravsyre og 2-phosphonbutan- 1,2,4-tricarbonsyre.As hydroxyalkanediphosphonic acid of formula I, e.g. 1-hydroxypropane, 1-hydroxybutane, 1-hydroxypentane, 1-hydroxyhexane-1,1-diphosphonic acid and 1-hydroxy-1-phenylmethane-1,1-diphosphonic acid and preferably 1-hydroxyethane-1,1-diphosphonic acid are used. . As phosphonic acid 5 of the general formula II, e.g. These are: 1-aminoethane, 1-amino-1-phenylmethane, dimethylaminoethane, dimethylaminobutane, diethylaminomethane, propyl and butylaminomethane-1,1-diphosphonic acid. Examples of phosphonic acids of general formula III are amino trimethylenephosphonic acid, ethylenediaminetetramethylene phosphonic acid, diethylene = 10 triamine pentamethylene phosphonic acid, aminotri- (2-propylene-2-phosphone = acid). Phosphonic acids of general formula IY may be used phosphonic succinic acid, 1-phosphonic l-methyl succinic acid and 2-phosphonic butane 1,2,4-tricarboxylic acid.
15 I stedet for de anførte phosphonsyrer kan der også anvendes deres vandopløselige salte, såsom natrium-, kalium-, ammonium- eller alkanolaminsalte. Phosphonsyrerne eller vandopløselige salte anvenae fortrinsvis i en mængde på 0,001 til 0,05 g/l. De kan anvendes enkeltvis eller i blanding. Særlig god har vist sig en blanding af 20 1-hydroxyethan-l,1-diphosphonsyre og aminotrimethylenphosphonsyre i vægtforholdet 4 : 1 til 1:4.Instead of the listed phosphonic acids, their water-soluble salts can also be used, such as sodium, potassium, ammonium or alkanolamine salts. The phosphonic acids or water-soluble salts are preferably used in an amount of 0.001 to 0.05 g / l. They can be used individually or in admixture. Particularly good has been found a mixture of 20 1-hydroxyethane-1,1-diphosphonic acid and aminotrimethylene phosphonic acid in the 4: 1 to 1: 4 weight ratio.
Opløsningerne indeholdende phosphonsyrerne eller deres salte bliver, hvis det er nødvendigt, indstillet på en pH-værdi af 5 til 6,5. Denn 25 indstilling kan ske med ammoniak eller eddikesyre.The solutions containing the phosphonic acids or their salts are adjusted, if necessary, to a pH of 5 to 6.5. This setting can be done with ammonia or acetic acid.
Til fremstilling af opløsningerne kan anvendes normalt vand, der hverken er fuldt afsaltet eller afhærdet. Når der til fremstilling af opløsningerne anvendes fuldt afsaltet eller destilleret eller 30 meget blødt vand, kræves en tilsætning af calciumioner. Fortrinsvis kan anvendes vandopløselige calciumsalte, såsom CaC^ eller Ca(NO^) Molforholdet calciumioner : phosphonsyrer skal være mindst 2:1.To prepare the solutions, normal water that is neither fully desalinated nor cured can be used. When fully desalted or distilled or very soft water is used to prepare the solutions, an addition of calcium ions is required. Preferably water-soluble calcium salts such as CaCl 2 or Ca (NO 2) may be used. The molar ratio of calcium ions: phosphonic acids must be at least 2: 1.
I almindelighed er det fordelagtigt at anvende et højere forhold mellem calciumioner og phosphonsyrer på ca. 5 : 1 til ca. 500 : 1.In general, it is advantageous to use a higher ratio of calcium ions to phosphonic acids of approx. 5: 1 to approx. 500: 1.
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En foretrukken udførelsesform for fremgangsmåden består i, at der til tætningsopløsningerne yderligere sættes en dextrin i en mængde på 0,1 til 5 g/l, fortrinsvis 0,1 til 2 g/l. Hertil anvendes især dextriner med en viskositet på 50 til 400 cP i 50 %ig opløsning ved 4n 20°C. Viskositeten er målt med et Brookfield-rotationsviskosimeter.A preferred embodiment of the process consists in further adding to the sealing solutions a dextrin in an amount of 0.1 to 5 g / l, preferably 0.1 to 2 g / l. In particular, dextrins having a viscosity of 50 to 400 cP are used in 50% solution at 4n 20 ° C. Viscosity is measured with a Brookfield rotational viscometer.
150715 6 I de følgende eksempler er aluminiumlegeringerne betegnet efter DIN 1725. Kvaliteten af oxidlaget blev bestemt ved den såkaldte tilsyneladende ledningsværdi efter DIN 50.949 og ved tabsfaktoren d efter DIN-udkast 50.920.In the following examples, the aluminum alloys are designated 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 DIN draft 50.920.
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Eksempel 1 Åluminiumprofiler (AlMg^), der på sædvanlig måde var affedtet alkalisk og bejset og derefter var blevet oxideret anodisk ved jævn-10 strøm-svovlsyre-metoden (lagtykkelse 22 .yin), blev tætnet med en opløsning af 0,003 g/1 l-hydroxyethan-l,l-diphosphonsyre og 0,5 g/l dextrin (viskositet 100 cP, målt i 50 %ig opløsning ved 20°C) i vand med 15°dH, som med ammoniak var indstillet til en pH-værdi på 5,8, ved 100°C i 70 minutter. Profilerne udviste ingen sealingbelægning, 15 lagtykkelsen var uforandret, og den tilsyneladende ledningsværdi (y = 8,5) og tabsfaktoren (d = 0,4l) viste en god tætning. Selv efter længere tids brug viste der sig i tætningsopløsningen ingen faste udfældninger af vandets hårdhedsdannere. Der dannedes et fnugget, tungt bundfald, som ikke afsatte sig på profilerne, og som let 20 kunne fjernes fra badet ved udsprøjtning.Example 1 Aluminum profiles (AlMg 2), which were conventionally degreased alkaline and stained and then oxidized anodically by the steady-stream sulfuric acid method (layer thickness 22 µm), were sealed with a solution of 0.003 g / l -hydroxyethane-1,1-diphosphonic acid and 0.5 g / l dextrin (viscosity 100 cP, measured in 50% solution at 20 ° C) in water with 15 ° dH adjusted with ammonia to a pH of 5.8, at 100 ° C for 70 minutes. The profiles showed no sealing coating, the layer thickness was unchanged, and the apparent conductivity (y = 8.5) and the loss factor (d = 0.4l) showed a good seal. Even after prolonged use, there were no solid deposits of water hardeners in the sealing solution. A fluffy, heavy precipitate formed which did not settle on the profiles and which could easily be removed from the bath by spraying.
Det samme resultat blev opnået, når der i stedet for 1-hydroxyethan- 1,1-diphosphonsyre blev anvendt di-, tri- og tetranatrium- eller kalium- eller ammoniumsaltene eller et triethanolaminsalt. Indstil-25 lingen af pH-værdien blev udført med eddikesyre, hvor det drejede sig om de alkaliske salte.The same result was obtained when instead of 1-hydroxyethane-1,1-diphosphonic acid, the di, tri and tetrasodium or potassium or ammonium salts or a triethanolamine salt were used. The adjustment of the pH was carried out with acetic acid, in the case of the alkaline salts.
Eksempel 2 30 På sædvanlig måde affedtet aluminiumblik (AlSi^), som var blevet oxideret anodisk ved jævnstrøm-svovlsyre-oxalsyre-metoden (lagtykkelse 21 ym), blev tætnet med en opløsning af 0,007 g/l l-hydroxy= ethan-1,1-diphosphonsyre i afioniseret vand under tilsætning af 10 mg/1 calciumioner og indstillingen af pH-værdien på 5,6 med 35 ammoniak ved 100°C i 60 minutter.Example 2 Ordinarily, degreased aluminum sheet (AlSii), which had been oxidized anodically by the DC-sulfuric acid-oxalic acid method (layer thickness 21 µm), was sealed with a solution of 0.007 g / l of 1-hydroxy = ethane-1. 1-diphosphonic acid in deionized water with the addition of 10 mg / l calcium ions and the adjustment of the pH of 5.6 with 35 ammonia at 100 ° C for 60 minutes.
Blikkene udviste ingen sealingbelægning,og tilsyneladende ledningsværdi (y = 12) og tabsfaktor (d = 0,49) viste en god tætning. Samme resultater kunne opnås med di-, tri- og tetraalkalimetal- eller airuno-40 riiumsalte.The gaze showed no sealing coating, and apparent conductivity (y = 12) and loss factor (d = 0.49) showed good sealing. The same results could be obtained with di-, tri- and tetra-alkali metal or airuno-sodium salts.
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Eksempel 5 På sædvanlig måde alkalisk affedtede og hejsede aluminiumprofiler (AlMgSiO,5), som var blevet oxideret anodisk ved en autocolor-metode 5 (lagtykkelse 18 ym), blev tætnet i 60 minutter ved 100°C i en opløsning af 0,005 g/1 l-hydroxyethan-l,l-diphosphonsyre, 0,005 g/l aminotrimethylenphosphonsyre og lg/l dextrin (viskositet 200 cP, målt i 50 %ig opløsning ved 20°C) i vand af 35°dH, indstillet med ammoniak til en pH-værdi på 5,9. Profilerne viste ingen sealingbe-10 lægning, og en god tætning påvistes af en tilsyneladende ledningsværdi (y = 10,5) og tabsfaktor (d = 0,47). Vandets hårdhed gjorde sig ikke generende bemærket under fremgangsmåden, da udfældninger af hårdhedsdarinere kun dannedes i form af fnuggede, let afsættelige bundfald, der ikke aflejrede sig på de tætnede dele,men på bunden af 15 badet.Example 5 As usual, alkaline degreased and hoisted aluminum profiles (AlMgSiO, 5) which had been anodically oxidized by an autocolor method 5 (layer thickness 18 µm) were sealed for 60 minutes at 100 ° C in a solution of 0.005 g / l. 1-hydroxyethane-1,1-diphosphonic acid, 0.005 g / l aminotrimethylene phosphonic acid and lg / l 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 demonstrated by an apparent conductivity (y = 10.5) and loss factor (d = 0.47). The hardness of the water was not bothered to notice during the process, as precipitates of hardness dariners formed only in the form of fluffy, easily settable precipitates which did not settle on the sealed parts but on the bottom of the bath.
Praktisk taget samme resultater blev opnået, når der i stedet for de førnævnte phosphonsyrer blev anvendt deres alkalimetal-eller anmonium-salte, idet de alkalisk reagerende salte blev indstillet ved hjælp a eddikesyre til en pH-værdi mellem 5,8 og 6,0.Virtually the same results were obtained when the alkaline metal or anmonium salts were used instead of the aforementioned phosphonic acids, the alkaline reacting salts being adjusted by acetic acid to a pH between 5.8 and 6.0.
Eksempel 4Example 4
Aluminiumprofiler (AlMgSi0,5), der på sædvanlig måde var affedtet alkalisk og bejset, blev oxideret anodisk ved jævnstrøm-svovlsyre-25 , x metoden (lagtykkelse 20-22 ym). Profilerne blev eftertætnet i en opløsning, der indeholdt 0,01 g/l l-hydroxyethan-l,l-diphosphonsyre og 2 g/l dextrin (viskositet 150 cP, målt i 50 %ig opløsning ved 20°C) i vand af 20°dH, indstillet med ammoniak til en pH-værdi ρβά 5,8 ved 98 til 100°C i 60 minutter. Profilerne udviste ingen sealing 30 , .Aluminum profiles (AlMgSi0.5), which were conventionally degreased alkaline and stained, were oxidized anodically by the direct-sulfuric acid-25, x method (layer thickness 20-22 µm). The profiles were sealed in a solution containing 0.01 g / L of 1-hydroxyethane-1,1-diphosphonic acid and 2 g / L of dextrin (viscosity 150 cP, measured in 50% solution at 20 ° C) in water of 20 ° dH, adjusted with ammonia to a pH value ρβά 5.8 at 98 to 100 ° C for 60 minutes. The profiles showed no sealing 30 ,.
belægning, og den tilsyneladende ledningsværdi (y = 9,0) og tabsfaktor (d = 0,40) viste en god tætning. Der optrådte ingen forstyrrelse som følge af vandets hårdhedsdannere.coating, and the apparent conduction value (y = 9.0) and loss factor (d = 0.40) showed a good seal. No disturbance occurred as a result of the hardness of the water.
Eksempel 5 På samme måde som beskrevet i eksempel 4 blev aluminiumprofiler tætnet i opløsninger, som i stedet for l-hydroxyethan-l,l-diphosphon-syre indeholdt en af de følgende phosphonsyrer i samme mængde: 40Example 5 In the same way as described in Example 4, aluminum profiles were sealed in solutions containing, instead of l-hydroxyethane-1,1-diphosphonic acid, one of the following phosphonic acids in the same amount: 40
Claims (3)
Applications Claiming Priority (2)
| 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 |
| DE2211553 | 1972-03-10 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| DK150715B true DK150715B (en) | 1987-06-01 |
| DK150715C DK150715C (en) | 1987-12-28 |
Family
ID=5838488
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK089173A DK150715C (en) | 1972-03-10 | 1973-02-20 | PROCEDURE FOR SEALING ANODICALLY GENERATED OXIDE LAYERS ON ALUMINUM OR ALUMINUM ALLOYS |
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 |
| NO131208B (en) | 1975-01-13 |
| 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 |
| 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 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUP | Patent expired |