EP0354365B1 - Verfahren zur elektrolytischen Metallsalzeinfärbung von anodisierten Aluminiumoberflächen - Google Patents

Verfahren zur elektrolytischen Metallsalzeinfärbung von anodisierten Aluminiumoberflächen Download PDF

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Publication number
EP0354365B1
EP0354365B1 EP89112556A EP89112556A EP0354365B1 EP 0354365 B1 EP0354365 B1 EP 0354365B1 EP 89112556 A EP89112556 A EP 89112556A EP 89112556 A EP89112556 A EP 89112556A EP 0354365 B1 EP0354365 B1 EP 0354365B1
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Prior art keywords
tin
acid
salts
metal salts
electrolyte
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Expired - Lifetime
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EP89112556A
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German (de)
English (en)
French (fr)
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EP0354365A1 (de
Inventor
Dieter Dr. Brodalla
Jürgen Lindener
Loert Dr. De Riese-Meyer
Willi Dr. Wüst
Christine Schröder
Willi Dr. Buchmeier
Jürgen Föll
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to AT89112556T priority Critical patent/ATE88510T1/de
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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
    • C25D11/20—Electrolytic after-treatment
    • C25D11/22—Electrolytic after-treatment for colouring layers

Definitions

  • the present invention relates to a process for the electrolytic metal salt coloring of anodized surfaces of aluminum and aluminum alloys, a defined oxide layer being produced by means of direct current in an acidic solution and then colored by means of alternating current using an acidic electrolyte containing tin (II) salts.
  • aluminum is known to be coated with a natural oxide layer, the layer thickness of which is generally less than 0.1 ⁇ m (Wernick, Pinner, Zurbrügg, Weiner; "The surface treatment of aluminum", 2nd edition, Eugen Leuze Verlag, Saulgau / Württ., 1977).
  • Significantly thicker oxide layers can be obtained by electrolytically oxidizing aluminum. This The process is known as anodizing, in older parlance also anodizing. Sulfuric acid, chromic acid or phosphoric acid is preferably used as the electrolyte. Organic acids such as oxalic, maleic, phthalic, salicylic, sulfosalicylic, sulfophthalic, tartaric or citric acid are also used in some processes.
  • the oxide layer consists of a relatively compact, depending on the anodizing conditions up to 0.15 ⁇ m thick barrier layer directly on the metallic aluminum, on which there is a porous, X-ray amorphous cover layer.
  • the anodization is usually carried out in 10 to 20% sulfuric acid at a voltage of 10 to 20 V and the resulting current density and a temperature of 18 to 22 ° C within 15 to 60 minutes, depending on the desired layer thickness and intended use.
  • the oxide layers produced in this way have a high absorption capacity for a large number of different organic and inorganic dyes.
  • the colored Al oxide surfaces are compacted by boiling in water for a long time or by treatment with superheated steam. This changes the Oxide layer on the surface in a hydrate phase (AlOOH), whereby the pores are closed due to volume increase. Due to its high mechanical strength, the "compressed" Al oxide layer offers a good protective effect for the enclosed dyes and the underlying metal.
  • the adsorptive coloring is based on the incorporation of organic dyes into the pores of the anodizing layer.
  • Methods for inorganic adsorptive staining are also known. They can be divided into single-bath and multi-bath processes. In the single-bath process, the Al part to be colored is immersed in a heavy metal salt solution, the corresponding colored oxide or hydroxide hydrate being deposited in the pores by hydrolysis.
  • the component to be colored is immersed in solutions of the reactants, which then individually penetrate into the pores of the oxide layer and form the color pigment here.
  • solutions of the reactants which then individually penetrate into the pores of the oxide layer and form the color pigment here.
  • a further disadvantage of the adsorptive processes is that the pigments only penetrate into the outermost layer area, so that the color can quickly fade due to abrasion under mechanical stress.
  • Electrolytic coloring processes have been known since the mid-1930s, in which anodized aluminum can be colored in heavy metal salt solutions by treatment with alternating current.
  • the elements of the first transition series such as Cr, Mn, Fe, Co, Ni, Cu and especially Sn are used here.
  • the heavy metal salts are mostly used as sulfates, with a pH of 0.1 to 2.0 being set with sulfuric acid. You work at a voltage of about 10 to 25 V and the resulting current density.
  • the counter electrode can either consist of graphite or stainless steel or of the same material that is dissolved in the electrolyte.
  • the heavy metal pigment is deposited into the pores of the anodic oxide layer in the half period of the alternating current, in which aluminum is the cathode, while in the second half period the aluminum oxide layer is further strengthened by anodic oxidation.
  • the heavy metal is deposited on the bottom of the pores, causing the oxide layer to color.
  • a problem with the coloring in tin electrolytes is the easy oxidizability of the tin, which leads to precipitations of basic tin (IV) oxide hydrates (tin acid) when used and, if necessary, even when the Sn solutions are stored.
  • Aqueous tin (II) sulfate solutions are known to be already oxidized to tin (IV) compounds through the action of atmospheric oxygen. This is very undesirable when coloring in tin electrolytes of anodized aluminum, because on the one hand it interferes with the process flow (frequent renewal or replenishment of the solutions which are unusable due to the formation of precipitation) and on the other hand leads to considerable additional costs due to the tin (IV) compounds which cannot be used for coloring.
  • a number of processes have therefore been developed which differ in particular in the type of stabilization of the mostly sulfuric acid tin (II) sulfate solutions for the electrolytic aluminum coloring.
  • DE-OS 28 50 136 proposes adding iron (II) salts from the group of sulfuric acid, sulfonic acids and amidosulfonic acids as stabilizers for the tin (II) compounds to the electrolyte containing tin (II) salts.
  • Sulfamic acid (amidosulfonic acid) or its salts are also frequently used alone or in combination with other stabilizers (JP-OSen 75 26066, 76 122637, 77 151643, 59 190 389, 54 162637; 79 039254; GB-PS 14 82 390) .
  • polyfunctional phenols such as the diphenols hydroquinone, pyrocatechol and resorcinol (JP-OSen 58 113391, 57 200221; FR-PS 23 84 037) and the triphenols phloroglucin (JP-OS 58 113391), pyrogallol (SA Pozzoli, F. Tegiacchi; Corrosive corrosion protection Alum., Event Eur. Foed. Korros., Vortr. 88th 1976 , 139-45; JP-OSen 58 113391; 57 200221) or gallic acid (JP-OS 53 13583) have already been described in this connection.
  • SA Pozzoli F. Tegiacchi
  • Corrosive corrosion protection Alum. Event Eur. Foed. Korros., Vortr. 88th 1976 , 139-45; JP-OSen 58 113391; 57 200221
  • gallic acid JP-OS 53 13583
  • DE-PS 36 11 055 describes an acidic Sn (II) -containing electrolyte with the addition of at least one soluble diphenylamine or substituted diphenylamine derivative, which stabilizes the Sn (II) and gives faultless colorations.
  • reducing agents such as thioethers or alcohols (DE-OS 29 21 241), glucose (HU-PS 34779), thiourea (JP-OS57 207197), formic acid (JP-OS 78 19150), formaldehyde (JP-OSes) are sometimes used 75 26066, 60 56095; FR-PS 23 84 037), thiosulfates (JP-OSen 75 26066, 60 56095), hydrazine (HU-PS 34779; JP-OS 54 162637) and boric acid (JP-OSen 59 190390, 58 213898) ) used alone or in combination with the aforementioned stabilizers.
  • thioethers or alcohols DE-OS 29 21 241
  • glucose HU-PS 34779
  • thiourea JP-OS57 207197
  • formic acid JP-OS 78 19150
  • formaldehyde JP-OSes
  • JP-OSes
  • complexing agents such as ascorbic, citric, oxalic, lactic, malonic, maleic and tartaric acid are also used (JP-OSen 75 26066, 77 151643, 59 190389, 60 52597 57 207197 54 162637, 54 097545, 53 022834 79, 039254 74 028576, 59 190390 58 213898, 56 023299; HU-PS 34779; FR-PS 23 84 037).
  • Another important problem in electrolytic coloring is the so-called scattering ability (depth scattering), which is the product property of coloring anodized aluminum parts that are at different distances from the counterelectrode with a uniform color.
  • Good spreadability is particularly important if the aluminum parts used have a complicated shape (coloring of the depressions), if the aluminum parts are very large and if, for economic reasons, many aluminum parts are colored in one process and medium shades are to be achieved. In application, therefore, a high spreadability is very desirable, since incorrect productions are avoided and the optical quality of the colored aluminum parts is generally better.
  • the process is more economical thanks to good spreadability, since more parts can be colored in one operation.
  • the uniformity concerns a coloring with the least possible local disturbances in the color (spotty coloring). Poor uniformity is mostly due to impurities such as nitrate or process errors in the anodization. A good staining electrolyte must under no circumstances impair the uniformity of the coloring.
  • a dyeing process can achieve good uniformity and still have poor spreading power; the reverse is also possible.
  • the uniformity is generally only influenced by the chemical composition of the electrolyte, while the scatterability also depends on electrical and geometric parameters, such as the shape of the workpiece or its positioning and size.
  • DE-OS 26 09 146 describes a process for coloring in tin electrolytes, in which the scattering ability is set by the special circuit and voltage arrangement.
  • DE-OS 20 25 284 describes that the use of tin (II) ions alone increases the scatterability, especially if tartaric acid or ammonium tartrate is added to improve the conductivity.
  • the tin (II) coloring has a tertiary current distribution (the current distribution is mainly determined by surface resistances and not by the conductivity of the electrolyte).
  • DE-PS 24 28 635 describes the use of a combination of tin (II) and zinc salts with the addition of sulfuric acid and additionally boric acid and aromatic carboxylic and sulfonic acids (sulfophthalic acid or sulfosalicylic acid).
  • good spreadability should be achieved when the pH is between 1 and 1.5. Setting the pH to 1 to 1.5 is a basic requirement for good electrolytic coloring; the pH value cannot be decisive for a particular improvement in the spreadability. It is not described whether the added organic acids have an effect on the spreadability. The spreadability achieved is also not quantitatively recorded.
  • DE-PS 32 46 704 describes a process for electrolytic coloring in which good scattering capacity is ensured by using a special geometry in the dye bath.
  • cresol and phenol sulfonic acid, organic substances such as dextrin and / or thiourea and / or gelatin are intended to ensure uniform coloring.
  • the disadvantage of this method is the high investment that is required for the creation of the mechanical devices.
  • deposition inhibitors such as dextrin, thiourea and gelatin has only a minor influence on the scatterability, since the deposition process in electrolytic dyeing differs significantly from that in galvanic tinning. A possibility of measuring the improvements in the spreading capacity is also not given here.
  • the present invention has for its object to provide an improved process for the electrolytic metal salt coloring of anodized surfaces of aluminum and aluminum alloys, wherein firstly a defined oxide layer is generated by means of direct current in acidic solution and then this is achieved by means of alternating current or alternating current superimposed on it using tin ( II) salts containing acidic electrolytes.
  • the object of the present invention was to largely protect the tin (II) salts contained in the electrolyte from oxidation to tin (IV) compounds by adding suitable compounds which do not have the abovementioned disadvantages.
  • Another object of the present invention was, in combination with new compounds which stabilize the tin (II) salts, to additionally improve the scatterability in the electrolytic metal salt coloring.
  • the added compounds should serve to replenish the used bath solutions required concentrated Sn (II) sulfate solutions (up to 200 g Sn 2+ / 1) to improve their storage stability.
  • the variation in the chain lengths is to be understood to mean that the compounds to be used according to the invention are sufficiently water-soluble.
  • the compounds stabilizing tin (II) salts used according to the invention have no waste water problems with regard to highly toxic waste water.
  • electrolytes which preferably contain 0.1 to 2 g / l of the compounds of the formulas (I) to (IV) which stabilize the tin (II) salts.
  • Another preferred embodiment of the present invention is that as a stabilizing Substance in the above concentrations 2-tert-butyl-1,4-dihydroxybenzene (tert-butylhydroquinone), methylhydroquinone, trimethylhydroquinone, 4-hydroxy-2,7-naphthalene-disulfonic acid and / or p-hydroxyanisole is used.
  • tert-butylhydroquinone 2-tert-butyl-1,4-dihydroxybenzene
  • methylhydroquinone methylhydroquinone
  • trimethylhydroquinone 4-hydroxy-2,7-naphthalene-disulfonic acid and / or p-hydroxyanisole
  • 1 to 50 g / l, preferably 5 to 25 g / l, p-toluenesulfonic acid and / or 2-naphthalenesulfonic acid can be added to the electrolyte to improve the scatterability.
  • the dyeing is usually carried out with the aid of a tin (II) sulfate solution which contains about 3 to 20 g, preferably 7 to 16 g, of tin per liter. It is colored at a pH of 0.35 to 0.5, corresponding to 16 to 22 g of sulfuric acid per liter, at a temperature of about 14 to 30 ° C.
  • the alternating voltage or alternating current superimposed on direct current (50 Hz) is preferably set at 10 to 25 V, preferably 15 to 18 V with an optimum of approximately 17 V ⁇ 3 V.
  • direct current superimposed on alternating current is equivalent to an alternating current superimposed on direct current.
  • the value of the terminal voltage is given in each case.
  • the coloring starts with a resulting current density of mostly about 1 A / dm2, which then drops to a constant value of 0.2 to 0.5 A / dm2.
  • metal concentration in the dyebath and dipping times different tones are obtained, which can vary between champagne-colored and various bronze tones to black.
  • the method of the present invention is characterized in that the electrolyte additionally contains 0.1 to 10 g / l iron, preferably in the form of iron (II) sulfate.
  • the method of the present invention is characterized in that the electrolyte contains further heavy metal salts in addition to tin, for example nickel, cobalt, copper and / or zinc (see Wernick et al, loc. Cit.).
  • the sum of the heavy metal ions - including tin - is preferably in the range from 3 to 20 g / l, in particular in the range from 7 to 16 g / l.
  • such an electrolyte contains 4 g / l Sn (II) ions and 6 g / l Ni (II) ions, both in the form of sulfate salts.
  • Such an electrolyte shows the same coloring properties as an electrolyte which contains only 10 g / l Sn (II) or only 20 g / l nickel.
  • One advantage is the lower wastewater pollution from heavy metal salts.
  • Fig. 1 gives a basic possibility of building a dye bath to assess the spreadability again, with the aluminum sheet serving as the working electrode. The other geometric factors can be seen in the figure.
  • aqueous electrolyte was prepared, each containing 10 g / l H2SO4 and SnSO4 and corresponding amounts of a stabilizer. 1 l solutions were stirred vigorously at room temperature with a magnetic stirrer and gassed with 12 l / h pure oxygen through a glass frit. The content of Sn (II) ions was continuously recorded iodometrically.
  • Table 2 show the results of the Sn (II) concentration change in dye baths under electrical stress.
  • An aqueous electrolyte was prepared which contained 10 g / l Sn (II) ions, 20 g / l H2SO4 and corresponding amounts of a stabilizer.
  • the permanent electrolysis was carried out with stainless steel electrodes.
  • the flowing amount of electricity was registered with an Ah counter.
  • the characteristic behavior of the oxide layer to be colored was simulated by corresponding sine distortion of the alternating current at high capacitive loads.
  • the amount of Sn (II) ions oxidized by electrode reactions was determined by continuous iodometric titration of the electrolyte and by gravimetric determination of the reductively deposited Sn and the difference between the sum of these two values and the starting amount of dissolved Sn (II).
  • the Ah value was chosen as a measure of the stabilizing effect, at which a reduction in the Sn (II) concentration by oxidative reaction at the electrodes by 5 g / l can no longer be prevented.
  • Test sheets of the dimensions 50 mm x 500 mm x 1 mm as shown in Fig. 1 from the DIN material Al 99.5 (material no. 3.0255) were conventionally pretreated (degreased, pickled, pickled, rinsed) and according to the GS process (200 g / l H2SO4, 10 g / l Al, air flow 8 m3 / m2 h, 1.5 A / dm2, 18 ° C) anodized for 50 min. The result was a layer build-up of approximately 20 ⁇ m.
  • the sheets pretreated in this way were colored electrolytically as described in the following examples.
  • the test panels were colored in a special test chamber for 135 s.
  • the dyeing voltage was varied between 15 and 21 V.
  • the dye bath contained 10 g / l Sn2+ and 20 g / l H2SO4 as a bath additive as well as different amounts of p-toluenesulfonic acid (3.1-3.3) or 2-naphthalenesulfonic acid (3.4) (10 g / l).
  • 10 g / l phenolsulfonic acid and in comparative example 3 10 g / l sulfophthalic acid were used accordingly.
  • the aim of the experiments should be to clarify the improvement in the depth scatter of the aluminum sheets colored in this way when p-toluenesulfonic acid and 2-naphthalenesulfonic acid are added to the dyebath.
  • the results of the deep scatter measurements with the addition of 0, 10 and 20 g / l p-toluenesulfonic acid and 2-naphthalenesulfonic acid at coloring tensions of 15, 18 and 21 V are shown in Tab. 3.
  • the tin distribution on the test sheet is measured at 10 different locations in the longitudinal direction.
  • the measurement is carried out with a scattered light reflectometer against the white standard TiO2 (99%).
  • Example 3 Analogously to Example 3, the dyebath according to Examples 3.2 and 3.3 contained 4 g / l Sn2+ and 6 g / l Ni2+ instead of 10 g / l Sn2+. The same results were obtained when measuring the litter.

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Electrochemical Coating By Surface Reaction (AREA)
  • Conductive Materials (AREA)
EP89112556A 1988-07-19 1989-07-10 Verfahren zur elektrolytischen Metallsalzeinfärbung von anodisierten Aluminiumoberflächen Expired - Lifetime EP0354365B1 (de)

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Application Number Priority Date Filing Date Title
AT89112556T ATE88510T1 (de) 1988-07-19 1989-07-10 Verfahren zur elektrolytischen metallsalzeinfaerbung von anodisierten aluminiumoberflaechen.

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DE3824403 1988-07-19
DE3824403A DE3824403A1 (de) 1988-07-19 1988-07-19 Verfahren zur elektrolytischen metallsalzeinfaerbung von anodisierten aluminiumoberflaechen

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EP0354365B1 true EP0354365B1 (de) 1993-04-21

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US (1) US5064512A (zh)
EP (1) EP0354365B1 (zh)
JP (1) JP2916168B2 (zh)
KR (1) KR960011248B1 (zh)
CN (1) CN1041446C (zh)
AR (1) AR241811A1 (zh)
AT (1) ATE88510T1 (zh)
AU (1) AU608992B2 (zh)
BR (1) BR8903541A (zh)
CA (1) CA1339115C (zh)
DD (1) DD284061A5 (zh)
DE (2) DE3824403A1 (zh)
DK (1) DK355689A (zh)
ES (1) ES2041899T3 (zh)
FI (1) FI89812C (zh)
HU (1) HU205973B (zh)
MX (1) MX173050B (zh)
NO (1) NO177233C (zh)
NZ (1) NZ229976A (zh)
PL (1) PL162190B1 (zh)
PT (1) PT91208B (zh)
SU (1) SU1722235A3 (zh)
TR (1) TR23878A (zh)
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DE4120415A1 (de) * 1991-06-20 1992-12-24 Henkel Kgaa Konfektioniertes zinn(ii)sulfat-granulat zur elektrolytischen metallsalzeinfaerbung
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DE4244021A1 (de) * 1992-12-24 1994-06-30 Henkel Kgaa Verfahren zur elektrolytischen Wechselstromeinfärbung von Aluminiumoberflächen
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US7347592B2 (en) * 2005-07-14 2008-03-25 Hewlett-Packard Development Company, L.P. Light source for a projection system having a light absorption layer
CN104651905B (zh) * 2015-01-28 2017-11-07 永保纳米科技(深圳)有限公司 一种阳极铝匀染缓染助剂及其操作液，和阳极铝匀染缓染处理工艺
US10669642B2 (en) * 2017-09-25 2020-06-02 Apple Inc. Using dispersion agents to chemically stabilize dyeing of metal parts
EP3553208A1 (de) * 2018-04-09 2019-10-16 DURA Operating, LLC Verfahren zum herstellen eines aluminiumbauteils mit einer farbigen oberfläche
CN108707942A (zh) * 2018-05-30 2018-10-26 江苏和兴汽车科技有限公司 一种铝合金黑色阳极氧化电泳的工艺
CN109468673A (zh) * 2018-12-16 2019-03-15 桂林理工大学 一种铝合金表面着色方法
TW202212640A (zh) 2020-04-24 2022-04-01 紐西蘭商西洛斯材料科學有限公司 在合金上施加著色塗層的方法
CN111876812B (zh) * 2020-08-01 2021-11-05 东莞市慧泽凌化工科技有限公司 一种无镍电解着色增黑添加剂及其使用方法
CN112301398B (zh) * 2020-09-29 2022-02-18 九牧厨卫股份有限公司 一种金色薄膜的制备方法
CN114351232A (zh) * 2022-01-14 2022-04-15 张家港扬子江冷轧板有限公司 一种电镀锡预电镀漂洗水循环系统及循环方法

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TR23878A (tr) 1990-10-16
JP2916168B2 (ja) 1999-07-05
YU46733B (sh) 1994-04-05
CN1039452A (zh) 1990-02-07
MX173050B (es) 1994-01-31
SU1722235A3 (ru) 1992-03-23
ZA895472B (en) 1990-03-28
NO177233B (no) 1995-05-02
HU205973B (en) 1992-07-28
NZ229976A (en) 1991-04-26
DK355689A (da) 1990-01-20
DE58904127D1 (de) 1993-05-27
FI893466A (fi) 1990-01-20
BR8903541A (pt) 1990-03-13
AR241811A1 (es) 1992-12-30
PT91208B (pt) 1995-03-01
AU3824289A (en) 1990-01-25
AU608992B2 (en) 1991-04-18
ATE88510T1 (de) 1993-05-15
FI89812C (fi) 1993-11-25
FI893466A0 (fi) 1989-07-18
NO177233C (no) 1995-08-09
FI89812B (fi) 1993-08-13
CA1339115C (en) 1997-07-29
EP0354365A1 (de) 1990-02-14
CN1041446C (zh) 1998-12-30
ES2041899T3 (es) 1993-12-01
PT91208A (pt) 1990-02-08
DE3824403A1 (de) 1990-01-25
KR960011248B1 (ko) 1996-08-21
DD284061A5 (de) 1990-10-31
NO892946L (no) 1990-01-22
JPH0273994A (ja) 1990-03-13
PL162190B1 (pl) 1993-09-30
DK355689D0 (da) 1989-07-18
HUT50888A (en) 1990-03-28
NO892946D0 (no) 1989-07-18
YU142989A (en) 1991-04-30
US5064512A (en) 1991-11-12
KR900001887A (ko) 1990-02-27

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