DE60010563T2 - Anodization method and device - Google Patents

Description

Technical part

The The present invention relates to a method for anodizing a metal body under vibratory stirring and an apparatus for carrying out this method.

State of the art

On the field of production of metal articles such as aluminum, an aluminum alloy, magnesium, a magnesium alloy, etc., the on the surface a metal body anodic applied by the anodization method have produced oxide film, which is the requirement that Reduce energy consumption and increase productivity and in particular to accelerate the anodizing process and the efficiency of the To improve oxide film formation. Next is the requirement that Anodization process under the condition to speed up that an anodizing bath at a higher temperature or room temperature is used.

Actually exists the most important problem with the conventional one Anodization in that a very long process time is required, even if a thinner oxide film with a thickness from 10 to 15 μm is formed. Therefore, the anodization process in the production line for the Metal articles, for example an anodized aluminum case window, using a plurality of parallel treatment devices take place in order to avoid a stoppage of the line, as the anodizing process approximately 10 to 15 times the duration claimed doe the pretreatment process and the aftertreatment process.

Of the The inventor has proposed an anodization method in which microbubbles with a diameter of 50 to 80 microns continuously over the surface to be treated of the aluminum body be guided whereby the anodization rate is 2 to 3 times the anodization rate in the conventional anodization process elevated. However, this method is in terms of treatment rate and the treatment temperature is still insufficient.

On the other hand, Japanese Unexamined Patent Publication No. Sho-60-9600 discloses an anodization method in which numerous bubbles having a diameter of 0.001 to 4 mm are generated by the aeration device in the electrolytic bath, and the bubbles are vibrated at a frequency of 10 exposed to 200 Hz and allowed to rise, so that the efficiency of the anodization process is improved. However, this method is still insufficient because oxygen produced by electrolysis at the anode tends to bubble and is released into the atmosphere and hence its oxidizing action on the metal body is reduced. In addition, the formation of oxygen bubbles leads to an increase in the electrical resistance at the surface of the metal body, so that a higher voltage is required for the treatment, so that a higher electrical power is required and thus increase the heat released and the energy loss. Accordingly, it is considered that this conventional method is used with a lower current density, for example, 2 to 3 A / dm ² , and thus it is not suitable for realizing the acceleration of the anodization process under the condition that the anodizing bath is at a higher temperature or Room temperature is used.

Presentation of the invention

A The object of the present invention is an anodization method with higher Anodization rate, lower energy consumption and higher efficiency oxide film formation available close.

A Another object of the present invention is an anodization method available too in which an excellent, uniform oxide film is obtained can, without the metal body to heat, even if the metal body is a complicated profile has.

• (a) Schritt, in dem das Anodisierbad durch eine Schwingrührvorrichtung bewegt wird, wobei das Anodisierbad durch ein Schwingrührwerk bewegt wird, indem ein Schwingblatt mit einer Amplitude von 0,5 bis 3,0 mm und einer Frequenz von 200 bis 800 Schwingungen pro Minute in Schwingungen versetzt wird; und
• (b) Schritt, in dem das Anodisierbad belüftet wird unter Verwendung von Luftblasen, die ein Diffusor erzeugt, der eine Porenöffnung von 10 bis 400 µm besitzt. Bei dem Anodisierungsverfahren kann der Anodisierungsvorgang erfolgen, während gleichzeitig wenigstens einer der folgenden Schritte (c) und (d) durchgeführt wird:
• (c) Schritt, in dem eine Schwingung auf den Metallkörper übertragen wird, wobei der Metallkörper mit einer Amplitude von 0,5 bis 1,0 mm und einer Frequenz von 100 bis 300 Schwingungen pro Minute in Schwingungen versetzt wird; und
• (d) Schritt, in dem der der Metallkörper eine Schwingbewegung ausführt, wobei der Metallkörper in eine Schwingbewegung mit einer Amplitude von 10 bis 100 mm und einer Schwingfrequenz von 10 bis 30 Schwingungen pro Minute versetzt wird.

In order to achieve the above object, according to a first aspect of the present invention, there is provided a method of anodizing a metal body comprising an anodization process in which an anodically-generated oxide film is formed on the surface of the metal body immersed in an anodizing bath Simultaneously carrying out the following steps (a) and (b):

• (a) a step in which the anodizing bath is agitated by a vibrating stirrer, the anodizing bath being agitated by a rocking agitator by applying an oscillating blade having an amplitude of 0.5 to 3.0 mm and a frequency of 200 to 800 cycles per minute Vibrations is added; and
• (b) Step in which the anodizing bath is aerated using air bubbles producing a diffuser having a pore opening of 10 to 400 μm. In the anodization process, the anodization process may be performed while performing at least one of the following steps (c) and (d):
• (c) a step of vibrating the metal body, vibrating the metal body with an amplitude of 0.5 to 1.0 mm and a frequency of 100 to 300 vibrations per minute; and
• (D) step in which the metal body performs a swinging motion, wherein the metal body is placed in a swinging motion with an amplitude of 10 to 100 mm and an oscillation frequency of 10 to 30 oscillations per minute.

• (A) Schwingrührvorrichtung für das Anodisierbad, die ein schwingungserzeugendes Mittel umfasst enthaltend einen Schwingungsmotor, ein Schwingrührmittel, um ein Schwingblatt mit einer Amplitude von 0,5 bis 3,0 mm und einer Schwingungsfrequenz von 200 bis 800 Schwingungen pro Minute in Schwingungen zu versetzen, um im Anodisierbad einen Schwingungsfluss zu erzeugen, wobei das Schwingblatt in einer oder mehreren Stufen an einem schwingenden Stab befestigt ist, der im Verbund mit dem schwingungserzeugenden Mittel in dem Anodisierbad schwingt, und ein Mittel zum Auffangen der Schwingbeanspruchung an einer Verbindungsstelle des schwingungserzeugenden Mittels und des Schwingrührmittels; und
• (B) Belüftungsvorrichtung für das Anodisierbad, die ein Verteilerrohr aus Keramik umfasst, das eine Porengröße von 10 bis 400 µm aufweist.

According to a second aspect of the present invention, there is provided an anodization method comprising an anodization process in which an anodically-generated oxide film is formed on the surface of a metal body immersed in an anodization bath, the anodization process being carried out while simultaneously receiving the following devices (A) and ( B) are operated:

• (A) Anodizing bath vibrating agitating apparatus comprising a vibration generating means including a vibration motor, a vibrating agitating means for vibrating a vibration blade having an amplitude of 0.5 to 3.0 mm and a vibration frequency of 200 to 800 vibrations per minute, to generate a vibration flux in the anodizing bath, the vibrating blade being fixed in one or more stages to a vibrating rod vibrating in association with the vibration generating means in the anodizing bath, and a means for absorbing the vibrational stress at a junction of the vibration generating means and the vibrating means vibrationally; and
• (B) Anodizing bath aerator comprising a ceramic manifold having a pore size of 10 to 400 μm.

The Device (A) further comprises an inverter for regulation the vibration motor of the device (A) to any frequency in the range of 10 to 500 Hz. The power of the vibration motor is suitable for a volume corresponding to the volume of the anodizing bath Value.

The Ceramic distributor tube of device (B) can have a porosity of 30 up to 40%. For example, in the case of a manifold, which is obtained by placing in a tube of a synthetic resin such as PVC many holes with a pore size of about 1 mm are formed, the electrolytic heat can not be dissipated effectively, because the bubbles are too big, and there is a dispersion of the electrical resistance of the System. In contrast, is in the ventilation device (B) according to the present Invention a porous Tube used in ceramic, and the above problem can thus be bypassed, i. Joule heat generated in the system can dissipated become. As a porous one Ceramic tube is preferably sintered at high temperatures Ceramic tube used as the basic substance alumina grains like ALUNDUM (trade name) contains. A suitable value for the pore size of the manifold is 10 to 400 μm, preferably at 10 to 120 μm, and the porosity (the ratio of pore area to the surface) is preferably from 30 to 40%. The outer diameter of the manifold is located typically 50 to 100 mm, and its length is typically included approximately 1000 to 1500 mm, but depending on the length of the treatment tank varied. The way in which the manifold is placed is not limited in a certain way, but if more manifolds are used, they are arranged so that the of the ventilation evenly distributed air bubbles around the metal body to move around. The distance between the distribution pipes is preferably 100 to 120 mm, and the distance in the vertical direction between the manifold and the metal body is preferably 100 to 300 mm. With such an arrangement leaves the ventilation across from the conventional one ventilation increase by 2 times.

• (C) Vorrichtung, um auf den Metallkörper über einen Elektrodenstab, an dem der Metallkörper aufgehängt ist, eine Schwingung mit einer Amplitude von 0,5 bis 1,0 mm und einer Frequenz von 100 bis 300 Schwingungen pro Minute zu übertragen; und
• (D) Vorrichtung, um auf einen Elektrodenstab, an dem der Metallkörper aufgehängt werden soll, eine Schwingbewegung zu übertragen, wodurch der Metallkörper vermittelt durch den Elektrodenstab eine Schwingbewegung ausführt mit einer Amplitude von 10 bis 100 mm und einer Frequenz von 10 bis 30 Schwingungen pro Minute.

In the anodization process, the anodization process may be performed while operating at least one of the following devices (C) and (D):

• (C) means to transmit to the metal body via an electrode rod, on which the metal body is suspended, a vibration with an amplitude of 0.5 to 1.0 mm and a frequency of 100 to 300 oscillations per minute; and
• (D) A device for transmitting an oscillating motion to an electrode rod to which the metal body is to be suspended, whereby the metal body mediates by the electrode rod to vibrate with an amplitude of 10 to 100 mm and a frequency of 10 to 30 Vibrations per minute.

The Device (C) may be equipped with a vibration motor, whose frequency is set by means of an inverter to 10 to 60 Hz is going to generate the vibration. The frequency (Hz) of the vibration motor the device (C) serving to vibrate the electrode rod to offset preferably at 50 to 65% of the frequency of the vibration motor the device (A). In particular, the frequency of the vibration motor the device (C) preferably 20 to 35 Hz. This vibration also displaces the metal body vibrates, but does not cause flow of the anodizing liquid.

The Swinging movement of the device (D), via the electrode rod, on the metal body suspended is, transferred is, has a vibration amplitude of preferably 20 to 60 mm.

According to one Third aspect of the present invention is an anodization device presented to perform the anodizing process, comprising the devices (A) and (B). The anodizing device can at least one of the devices (C) and (D).

According to the present invention, since the two apparatuses (A) and (B) are operated simultaneously, the anodizing operation can provide good stability with an increased current density of about 10 to 15 A / dm over the conventional anodizing operation using only the aeration apparatus ² and in a significantly reduced Anodisierungsbehandlungsdauer done. In the anodization process, the treatment temperature is an important factor that influences the energy cost of the process and the quality of the oxide film obtained. In the conventional anodization method, which is performed using the aeration, a temperature of -5 to 0 ° C is required to form a hard anodic oxide film, and a temperature of 20 ° C or less is anodic for the formation of a normal one oxide film to be preferred. On the other hand, according to the present invention, the formation of a hard anodic oxide film at a temperature of 10 to 20 ° C and the formation of a normal anodized oxide film can be carried out at a temperature of 30 to 35 ° C, resulting in a reduction in energy cost for cooling Anodisierbads leads and an excellent quality of the oxide film even at higher temperatures than prevail in the conventional method.

Of the Inventor has published in the Japanese Patent Application No. Hei-6-71544 and Japanese Publication No. Hei-6-220697 the use of a vibrating stirrer suggested in a plating bath. When galvanizing takes over the object to be electroplated the function of the cathode, and the metal ions that are released from the anode and in the plating bath are present, deposit on the cathode as a metal film. At the Galvanization is subject to water electrolysis, and to the surface of the Cathode produces hydrogen. The hydrogen tends to bubble, resulting in an increase in electrical resistance and a reduction the efficiency of the electric current leads, causing the deposition the metal ions are inhibited at the cathode and the duration of the electroplating process elevated becomes. In the above-mentioned published Japanese patent application Hei-6-71544 becomes the vibrating stirrer for the purpose of using the hydrogen from the surface of the Remove the cathode caused by the hydrogen bubbles To avoid inhibition of metal deposition.

In contrast, takes over in the anodizing process, the article to be treated, i. one Metal body, the function of the anode. This is the plating process opposite process. The hydroxide ions formed by electrolysis are attracted to the anode and decomposed by electrical discharge, whereby oxygen is created, which serves the surface of the Metal body, i.e. the anode, to oxidize, so that on the surface of the metal body forms an oxide film. Thus holds The oxygen is preferably around the anode. Accordingly it was considered that the use of the above vibrationally would be useless in an anodizing bath, because the Schwingrührvorrichtung The oxygen bubbles around the anode drive and thus the efficiency of the anodizing process.

Of the Inventor, however, has discovered, to his great surprise, that anodized oxide film of good density and uniformity with a higher one Anodization rate than in the conventional A method is formed when in the anodizing a Schwingrührvorrichtung is used. The consideration of the inventor is that in the case of using the vibrating stirring device (A) the oxygen produced by electrolysis does not form bubbles, but as nascent oxygen remains around the anode and with excellent Efficiency at the anode responds.

As mentioned above, are the plating process and the anodization process from each other different methods, and therefore the effect of use the aforementioned vibrating stirring device (A) in the anodization process not obvious in the context of the prior art.

Of the Metal body, i.e. the object to be treated in the anodizing process for example, aluminum, an aluminum alloy, magnesium, a magnesium alloy, titanium, a titanium alloy, niobium, a Niobium alloy, tantalum, a tantalum alloy, zirconium, a zirconium alloy, Lead or a lead alloy. Examples of aluminum alloys are Al-Si, Al-Mg, Al-Mg-Si and Al-Zn. The metal body can be a blind hole or a depression with a diameter of 10 mm or less or a through hole with a diameter of 10 mm or less.

The in the anodizing process according to the present invention Invention used anodizing, i. the electrolyte bath, is a acidic bath containing, for example, chromic acid, boric acid, boron ammonium, sulfuric acid, phosphoric acid, oxalic acid, benzenesulfonic acid, amidosulfuric acid, citric acid, tartaric acid, formic acid, succinic acid or a combination of these acids contains.

at the method according to the present invention Invention can be a pre-treatment process, as is usual before the anodizing process, respectively.

• (a) Entfetten – Reinigen mit Wasser
• (b) Entfetten – Reinigen mit Wasser (Beizen – Reinigen mit Wasser) – Dekapieren – Reinigen mit Wasser
• (c) Mechanisches Polieren – Entfetten – Reinigen mit Wasser
• (d) Mechanisches Polieren – Entfetten – Reinigen mit Wasser – Beizen – Reinigen mit Wasser – Dekapieren – Reinigen mit Wasser
• (e) Entfetten – Reinigen mit Wasser – elektrolytisches Polieren oder chemisches Polieren – Reinigen mit Wasser – Oxidentfernung oder Dekapieren – Reinigen mit Wasser
• (f) Mechanisches Polieren – Entfetten – Reinigen mit Wasser – elektrolytisches Polieren oder chemisches Polieren – Reinigen mit Wasser – Oxidentfernung oder Dekapieren – Reinigen mit Wasser

Examples of a pretreatment process are:

• (a) Degrease - Clean with water
• (b) degreasing - cleaning with water (pickling - cleaning with water) - picking - cleaning with water
• (c) Mechanical polishing - degreasing - cleaning with water
• (d) Mechanical polishing - degreasing - cleaning with water - pickling - cleaning with water - picking - cleaning with water
• (e) degreasing - cleaning with water - electrolytic polishing or chemical polishing - cleaning with water - oxide removal or pickling - cleaning with water
• (f) Mechanical polishing - degreasing - cleaning with water - electrolytic polishing or chemical polishing - cleaning with water - oxide removal or picking - cleaning with water

In the method according to the present invention Invention can be as usual after the anodizing process, a post-treatment process takes place. Examples of post-treatment processes belongs a compacting step for treating the porous surface of the metal body. Of the Compaction step can be carried out by means of steam, metal salt, electroplating, Dyes or pigments or a combination of these agents respectively.

Of the Sequence of operations pretreatment, anodization and post-treatment in the A method of anodizing a metal body of aluminum or a Aluminum alloy comprises the steps listed in Table 1 below, whereby at each step also the active substance and the conditions, under where the treatment was done will be called,

Table 1

Of the Degreasing step can be done by cleaning the metal body with an organic solvent like Gasoline or an aqueous one surfactant solution, with an aqueous Acid solution like 5 to 25 percent sulfuric acid (Mass concentration), with an aqueous base solution like 5 to 20 percent NaOH solution (Mass concentration), or with an aqueous phosphate solution.

Of the Pickling step can be by alkaline reaction with 5 to 25% NaOH (Mass concentration), by an alkaline phosphate reaction with 3 to 8% NaOH and 5 to 10% sodium phosphate (mass concentration) or by a reaction with chromium sulfate.

Of the Anodization step can take place at a ratio of 4 g / liter the metal body and the anodizing bath. In this step, phosphoric acid, oxalic acid, etc. or a combination of these acids instead of sulfuric acid be used. The duration of treatment varies according to the Thickness of the formed oxide film.

at the anodization method according to the present invention Invention is preferably at least one step, in particular the degreasing step and the compacting step, part of the Pretreatment or aftertreatment are performed while the Device (A) is operated. Preferably, at the same time operated the device (B). Preferably, at the same time at least one of the devices (C) and (D) operated.

If the vibratory stirring device (A) during of the anodizing step, the surface tension lowers of the anodizing bath, leaving on the surface of the metal body or of the object to be treated resulting active oxygen good with the metal body, i.e. the anode comes into contact to form bubbles above, and the surface of the metal body is oxidized at a rate several times, for example 5 times the speed in the conventional anodization process is, and it becomes anodized oxide film of excellent uniformity educated.

According to the present Invention moves a big one Number of bubbles formed by the ceramic manifold, in the Anodisierbad upwards, the entire object to be treated by wrapped in the bubbles becomes. The bubbles are then released to the outside. Therefore, the electrolytic heat (Joule heat) effectively absorbed by the bubbles, causing the object to be treated rapidly chilled and also air and dust from the micropores of the treated Can be removed be effectively discharged with the bubbles, so that on the treated Subject no deposits caused by heat and the Oxide film thus has excellent uniformity. So that Joule heat effectively dissipated is, is the amount of air supplied to an anodizing bath of 160 liters preferably at least 120 liters / min.

In the anodizing process, the reaction heat is produced by the anodic oxidation, and therefore The anodizing bath is cooled to keep its temperature constant. As a cooling device, a heat exchanger is used, and the anodizing is circulated through the heat exchanger.

It is known that the quality of the oxide film of γ-Al ₂ O ₃ · H ₂ O, which forms on the surface of the metal body made of aluminum or an aluminum alloy, deteriorates as the temperature of the anodizing bath increases. It is also known that the oxide film becomes cracked when the temperature of the anodizing bath is too low. The oxide film obtained according to the present invention is of better quality than anodic oxide film obtained by conventional methods under the same temperature conditions. In addition, the oxide film obtained according to the present invention, whose quality is better than that of a conventional anodized oxide film, can be obtained at temperatures higher by 10 to 15 ° C than in the conventional method.

at the method according to the present invention Invention is the temperature of the Anodisierbads for a normal aluminum oxide film at 35 ° C or lower, preferably at a room temperature of about 30 ° C; for a normal oxide film an aluminum alloy is 20 ° C or lower, preferably but at about 15 ° C; for one Hard oxide film is 10 to 15 ° C.

• (1) lässt sich die Behandlungsdauer des Anodisierungsvorgangs erheblich verkürzen, wobei die Anodisierungsrate gegenüber dem herkömmlichen Anodisierungsverfahren das 3- bis 5fache beträgt, ohne dass Ablagerungen durch Hitzewirkung entstehen, wodurch eine Energieeinsparung erreicht wird; die Behandlungsdauer des gesamten Vorgangs einschließlich des Vorbehandlungsvorgangs und des Nachbehandlungsvorgangs lässt sich weiter verkürzen, wenn die Vorrichtung (A) bei der Vorbehandlung oder bei der Nachbehandlung verwendet wird, wobei vorzugsweise auch die Vorrichtung (B) verwendet wird, und eine Verwendung der Vorrichtungen (C) und/oder (D) noch mehr zu bevorzugen ist;
• (2) weist der erhaltene anodisch erzeugte Oxidfilm eine größere Vickers-Härte auf;
• (3) weist der erhaltene anodisch erzeugte Oxidfilm eine exzellente Gleichmäßigkeit auf; somit ist die vorliegende Erfindung für die Herstellung von OPC-Trommeln von Vorteil;
• (4) kann der Anodisierungsvorgang bei einer um 5 bis 10 °C höheren Temperatur als beim herkömmlichen Verfahren durchgeführt werden, wobei ein Oxidfilm von gleichwertiger Qualität erhalten wird. Zum Beispiel sind beim herkömmlichen Verfahren zur Bildung eines harten anodisch erzeugten Oxidfilms Behandlungstemperaturen von –5 bis 5 °C und zur Bildung eines normalen anodisch erzeugten Films von ungefähr 20 °C erforderlich, während die vorliegende Erfindung Temperaturen von 10 bis 15 °C zur Bildung von harten anodisch erzeugten Oxidfilmen und 30 bis 35 °C zur Bildung von normalen anodisch erzeugten Oxidfilmen ermöglicht und somit die Verwendung einer Kühlvorrichtung mit niedrigerer Leistung ausreicht;
• (5) bildet sich selbst, wenn der Metallkörper Sacklöcher oder hindurchgehende Löcher mit einem Innendurchmesser von 10 mm oder weniger aufweist, problemlos ein anodisch erzeugter Oxidfilm auf der Oberfläche des Metallkörpers einschließlich der Innenflächen der Sacklöcher oder hindurchgehenden Löcher mit exzellenter Gleichmäßigkeit; somit ist die vorliegende Erfindung für die Herstellung von Metallartikeln mit kompliziertem Profil wie Platten mit unregelmäßiger Oberfläche, Maschinenteilen, Teilen von Wärmetauschern usw. von Vorteil;
• (6) weist der erhaltene anodisch erzeugte Oxidfilm hinsichtlich Glanz, Härte, Verschleißeigenschaften und Korrosionsbeständigkeit eine höhere Qualität auf als ein Oxidfilm, der nach dem herkömmlichen Verfahren bei derselben Behandlungstemperatur erhalten wird;
• (7) lässt sich die Menge der Luft, die dem Anodisierbad durch die Belüftung zugeführt wird, durch Kombination mit der Schwingrührvorrichtung stark erhöhen, so dass die Temperatur des Anodisierbads gesenkt und die Stromdichte erhöht werden kann, während beim herkömmlichen Verfahren ohne Verwendung der Schwingrührvorrichtung die durch die Belüftung zugeführte Luft auf einen niedriegeren Wert beschränkt ist, damit ein gleichmäßiger anodisch erzeugter Oxidfilm erhalten wird; und
• (8) lässt sich der erhaltene Oxidfilm gut färben.

In the method according to the present invention

• (1) the treatment time of the anodization process can be shortened considerably, the anodization rate being 3 to 5 times higher than that of the conventional anodization process without the occurrence of heat build-up, thereby achieving energy saving; the treatment time of the entire process including the pretreatment process and the after-treatment process can be further shortened when the apparatus (A) is used in the pre-treatment or post-treatment, preferably using the apparatus (B), and use of the apparatuses (C ) and / or (D) is even more preferable;
• (2) the resulting anodized oxide film has a larger Vickers hardness;
• (3) the obtained anodic oxide film has excellent uniformity; thus, the present invention is advantageous for the production of OPC drums;
• (4) The anodization process can be carried out at a temperature higher by 5 to 10 ° C than in the conventional method, thereby obtaining an oxide film of equivalent quality. For example, in the conventional method of forming a hard anodic oxide film, treatment temperatures of -5 to 5 ° C and formation of a normal anodized film of about 20 ° C are required, while the present invention requires temperatures of 10 to 15 ° C to form hard anodic oxide films and 30 to 35 ° C to form normal anodized oxide films and thus allows the use of a cooler with lower power sufficient;
• (5) even if the metal body has blind holes or through holes having an inner diameter of 10 mm or less, even if anodic oxide film is formed on the surface of the metal body including the inner surfaces of the blind holes or holes with excellent uniformity; thus, the present invention is advantageous for the production of metal articles having a complicated profile such as irregular surface plates, machine parts, heat exchanger parts, etc.
• (6) the resulting anodized oxide film has a higher quality in gloss, hardness, wear resistance, and corrosion resistance than an oxide film obtained by the conventional process at the same treatment temperature;
• (7) The amount of air supplied to the anodizing bath by the aeration can be greatly increased by combining with the vibrating agitator, so that the temperature of the anodizing bath can be lowered and the current density can be increased, whereas in the conventional method without using the vibrating agitator air supplied to the ventilation is restricted to a lower value to obtain a uniform anodic oxide film; and
• (8), the obtained oxide film can be colored well.

BRIEF DESCRIPTION OF THE DRAWINGS

1 Fig. 10 is a cross-sectional view showing an embodiment of an apparatus according to the present invention;

2 is a cross-sectional view showing the device 1 shows;

3 is a plan of the device 1 ;

4 Fig. 11 is a plan view of another embodiment of the apparatus according to the present invention;

5 is a side view showing the device 4 shows;

6 is a frontal view of the device 4 shows;

7 is a cross-sectional view along the line Y-Y in 6 ;

8th is a cross-sectional view taken along the line X-X in 5 ;

9 Fig. 10 is an enlarged cross-sectional view of a portion of a vibrating rod;

10 Fig. 10 is an enlarged cross-sectional view showing a manner in which vibration vanes can be fixed to a vibrating rod;

11 Fig. 11 is a plan view showing still another embodiment of a laterally oscillating vibratory stirring device;

12 is a cross-sectional view of 11 ;

13 Fig. 11 is a plan view showing still another embodiment of the apparatus according to the present invention;

14 is a side view of the device 13 ;

15 is a front view of the device 13 ;

16 shows a metal body hanging from an anode rod;

17 shows a metal body which is held by a holder;

18 is a plan view showing an arrangement of anode and cathode;

19 Fig. 11 is a plan view showing an arrangement of manifolds;

20 Fig. 10 is a block diagram of an anodization apparatus according to the present invention;

21 , Fig. 12 is a diagram showing the initial current density in the anodization process;

22 is a flowchart of a continuous treatment system;

23 shows a relationship between the hardness (Hv) of the obtained oxide film and the temperature of the anodizing bath; and

24 Figure 4 shows a manner of subdivision and measurement points on an anodized aluminum plate for evaluating the thickness and hardness of the oxide film.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

The 1 to 3 show an embodiment of the anodizing device according to the present invention, in which the devices (A) and (B) are present.

In the 1 to 3 The ventilation device (B) comprises three distribution pipes 12 resting on the bottom plate of the anodizing tank 1 are arranged, and inlet openings for compressed air 10 through which the distribution pipes 12 Compressed air is supplied. Denoted by the reference numerals 4 a vibration motor, 16 a swinging rod and 17 a swing leaf. These are parts of the vibratory stirring device (A).

The reference number 5 denotes an anode rod serving as a suspension member for an article or metal body (not shown) to be treated. The reference number 6 denotes a cathode rod, which serves as a suspension element for a cathode (not shown). The reference number 9 denotes a base member on which the anodizing tank 1 stands.

The manifold 12 , the anodizing tank 1 , the inlet openings for compressed air 10 , the vibration motor 4 , the swinging staff 16 , the swinging leaf 17 , the anode rod 5 , the cathode rod 6 and the base element 9 are substantially the same as those of the embodiments explained below.

In the 4 to 6 showing another embodiment, the devices (A), (B), (C) and (D) are present. The in the 4 to 6 shown Schwingrührvorrichtung showing the vibration motor 4 is included in the 7 and 8th shown.

The ventilation device (B) in the 4 to 6 includes two distribution pipes 12 resting on the bottom plate of the anodizing tank 1 are arranged, and inlet openings for compressed air 10 through which the distribution pipes 12 Compressed air is supplied.

The oscillating device (D) in the 4 to 6 is equipped with the vibration motor 3 , a swinging support frame 2 caused by the movement of the vibration motor 3 is vibrated, and a suspension element 5 which also serves as the anode rod and by means of the anode rod support 13 on the swinging support frame 2 is attached. An article to be subjected to the anodization treatment (hereinafter referred to as an article to be treated or a metal body) becomes electrically connected to the anode rod 5 connected and mechanically attached thereto. The oscillatory movement takes place slowly with an amplitude of 10 to 100 mm, preferably 20 to 60 mm and with a frequency of 10 to 30 oscillations per minute. The swinging support frame 2 swings in the right and left in the 4 and 5 defined direction, so that its lower section on guide elements 8th moved to the base element 9 are attached to which the vibration motor 3 is attached.

To a vibration on the swinging support frame 2 to transfer, becomes the vibration motor 14 at a suitable location on the swinging support frame 2 attached. The vibration of the vibration motor 14 puts the swinging support frame 2 in vibration, and the swinging motion of the swinging support frame 2 is transferred to the metal body, for example, a body made of aluminum, an aluminum alloy or the like. From these elements, the vibration transmission device (C) is formed. The vibration motor 14 generates by means of an inverter a vibration of 10 to 60 Hz, preferably from 20 to 35 Hz, and the oscillating support frame 2 is placed in a vibration with an amplitude of 0.5 to 1 mm and a frequency of 100 to 300 vibrations per minute.

The reference numbers 6 . 7 . 11 in 4 in this sequence, a cathode, a cathode holder and a heater.

An embodiment of the vibratory stirring device (A) for the anodizing bath is disclosed in US Pat 7 and 8th shown.

The vibrationally but is not on this embodiment limited. For example, you can Schwingrührvorrichtungen used as disclosed in Japanese Laid-Open Publication No. Hei-6-304461, Japanese Patent Laid-Open Publication No. Hei-6-312124 (corresponding to US Pat. No. 5,375,926) in Japanese Laid-Open Publication Hei-6-330395, in Japanese Laid-Open Publication Hei-8-173785, in Japanese Laid-Open Publication No. Hei-9-40482 and published Japanese Patent Application No. Hei-6-71544 disclosed by the present inventor Application were submitted.

As in the 7 and 8th shown is a basic vibrating element 40 at which the vibration motor 4 is firmly mounted, via a variety of coil springs 20 on the container 1 stored. Within each pen 20 there is a lower supporting pin 22 standing vertically with the anodizing tank 1 firmly connected, and an upper supporting pin 21 that with the basic oscillating element 40 is firmly connected and in the vertical direction on the lower supporting pin 22 is aligned. The upper end of the lower supporting pin 22 is a certain distance from the lower end of the upper supporting pin 21 separated.

9 shows an enlarged cross section of a part of a vibrating rod 16 who at the Ba sisschwingelement 40 is attached. Around the swinging staff 16 is at the junction between the base vibrating element 40 the vibration generating device and the vibrating rod a means for absorbing the vibration stress 19 available, which is formed by a rubber ring. The reference number 46 denotes a washer and the reference numerals 48 . 50 . 52 and 54 each designate a mother. The length of the rubber ring 19 is typically 3 to 8 times the diameter of the vibrating rod, and its outer diameter (size) is 1.3 to 3 times, but preferably about 1.5 to 2.5 times the diameter of the vibrating rod. When viewed from another angle, the swinging wand 16 is a round rod with a diameter of 10 to 16 mm, then lies the thickness of the rubber ring 19 preferably at 10 to 15 mm. When the diameter of the swinging rod (round rod) 20 to 25 is, then the thickness of the rubber ring is preferably 20 to 30 mm. If no rubber ring is used, there is a problem that the vibration stress around the joint between the base vibrating element 40 and the swinging staff 16 concentrated and the swinging rod can break easily. In this case, however, the above problem can be completely solved by firmly inserting the rubber ring.

On every swinging rod 16 in the 7 and 8th located between adjacent swing leaves 17 a spacer 30 , so that the leaves, each by a pair of vibration-leaf fastening elements 18 be kept at a certain distance from each other.

The swing leaf 17 is preferably made of thin metal, elastic synthetic resin, rubber or the like, and its thickness may be determined so that under the effect of the vertical vibration of the vibration motor 4 , by which the vibration is transmitted to the system or to the anodizing bath to stimulate a flow, at least the area of the tip of the blade shows a flutter phenomenon (as if it were wavy). As a material for a metal swinging can be titanium, aluminum, copper, steel, stainless steel or an alloy of these metals use. As the synthetic resin, use may be made of polycarbonate, a vinyl chloride-based resin, polypropylene or the like. The thickness is not limited to a certain value, but in order to transmit the vibrational energy and enhance the effect of the vibration, in the case of metal, it is preferably 0.2 to 2 mm, and in the case of plastics, 0.5 to select 10 mm. If the thickness is too large, the effect of vibrating stirring is reduced.

The swing leaves can at a height or at several heights be attached to the swinging rod. A variety of vibration vanes can be according to the depth of the anodising bath. If the number the heights elevated becomes and the load of the vibration motor increases too much, the Vibration amplitude is reduced and the engine heats up.

Further, all vibration vanes can be mounted perpendicular to the oscillating rod or shaft. However, it is preferable that they are fixed with an inclination angle of 5 to 30 degrees, preferably 10 to 20 degrees in the positive or negative direction, with the direction perpendicular to the oscillating rod being zero degrees (see FIG 7 and 10 ).

The vibration vane fixing element 18 and the swinging leaf 17 may be inclined and / or bent as a whole, viewed from the side of the vibrating shaft. Even if they are bent, they are preferably tilted by 5 to 30 degrees, with a total of 10 to 20 degrees being preferable.

The vibration leaves 17 are at the swinging bar 16 attached and thereby from the top and the bottom of the vane mounting hardware 18 clamped, whereby vibration blade sections are formed. In particular, in the oscillating rod 16 Threaded holes are formed around the leaves 17 to be fastened by means of screws. Preferably, the vibration vanes 17 but supportive of the oscillating blade attachment element 18 depressed so that they, as in 10 shown are clamped from above and below by the vibration vane fixing members; the vane blade attachment elements 18 then be with nuts 24 tightened to the vibration vanes 17 on the swinging rod 16 to fix.

If the vibration leaves can be inclined and / or bent the lowest or the two lowest vibration vanes of the plurality of vibration vanes after downwards and / or bent, while the other vibration vanes after tilted and / or bent above. With this construction, the stirring in the bottom area the Anodisierbads be made sufficiently effective, and the Occurrence of traps can be so prevent.

If only in the bottom area of the Anodisierbads should not be stirred, the down ge bent oscillating blades are removed. This measure is effective when unwanted components such as deposits, etc. are collected in the lower area and removed from the lower area, without these undesirable components are distributed in the container.

Around to prevent the discharge of the generated gas from the anodizing bath, it is preferable to tilt all swing leaves down or to bend.

The vibrating stirrer may be located at one end of the anodising container as shown in FIGS 1 to 3 and in the 13 to 15 is shown, wherein the reference numerals 28 . 29 and 30 designate the heater, the compressed air generator or the cathode holder. However, in order to enable the work with large containers, also at both ends of the Anodisierbehälters a vibrating stirring device may be present, as in the 4 to 10 is shown. Further, each vibratory stirring device as shown in the above-mentioned figures is constructed so that the vibrating blades are vibrated in a vertical direction. However, it can also be designed so that the direction of vibration is horizontal and the vibration vanes 17 in the bottom area of the anodizing tank 1 are arranged as disclosed in the aforementioned Japanese Patent Laid-Open Publication No. Hei-6-304461 or as shown in the 11 and 12 is shown, in which the reference numeral 25 denotes a vibration transmitting frame on which the vibration motor 4 is mounted, and the reference number 27 denotes a support spring. In this case, the weight of the left side with the vibration motor 4 and to balance the weight of the right side is preferably a counterweight 26 as in 12 shown arranged.

As in 1 shown, the vibration can 17 with a positional deviation to the center of the Anodisierbehälters 1 on the swinging rod 16 be attached to effectively increase the strength of the Schwingrührvorgangs in the anodizing.

The oscillating rod can be directly connected to the vibration motor for operation. However, as disclosed in the aforementioned Japanese Patent Laid-Open Publication No. Hei-6-304461 and Japanese Laid-Open Patent Publication Hei-6-330395, it can be operated so that the vibration of the vibration motor as shown in Figs 11 and 12 shown over the swing frame 25 on the swinging rod 16 is transmitted.

Next are located between the oscillating blade 17 and the vibration vane fixing member 18 , as in 10 shown, preferably films 23 from a fluorine-containing polymer, as this can significantly reduce the frequency of damage to the vibration vanes. The fluorine-containing polymer is polytetrafluoroethylene (PTFE), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride, ethylene / tetrafluoroethylene copolymer (ETFE), ethylene / Chlorotrifluoroethylene copolymer, propylene / tetrafluoroethylene copolymer or the like in question. Fluorine-containing rubber is preferable.

As in 16 shown is the metal body 62 when in the anodizing bath 64 treated by a keeper 60 clamped. The holder 60 includes a hook portion 60a which is attached to the anode rod 5 is mounted, a clip section 60b which is the upper section of the metal body 62 holds and a compression spring 60c that provides the power of the clip. The topmost section of the metal body 62 is located in the anodizing bath 64 , In the anodizing bath 64 be from the manifolds 12 Air bubbles generated. The metal body 62 will be together with the holder 60 transferred from a treatment tank to another treatment tank.

If the metal body 62 is of relatively low weight or small size, is another, in 17 shown type of holder 70 to prefer. The holder 70 includes a support frame 70a that is electrically and mechanically with the anode rod 5 to connect, and wires 70b to the metal body 62 on the support frame 70a to fix.

18 Fig. 11 is a plan view showing an example of the arrangement of anode and cathode in the anodizing bath. Each of the four cathodes 68a to 68d has the width w. The cathodes 68a . 68b and the cathodes 68c . 68d are electrically and mechanically with each other and with the others in 1 shown cathode rods 6 connected, and the distance between them is d1. The anode or the metal body 62 is in the middle between the four cathodes 68a to 68d arranged with the distance d2 or d3 (= d2).

19 Fig. 11 is a plan view showing an example of the arrangement of the ceramic distribution pipes in the anodizing tank. This arrangement is preferable, especially if the metal body 62 longer than the distribution pipes 12 is. A variety of distribution pipes 12 is at intervals r1, r2 from each other in the anodizing tank 1 arranged, whose walls they have the distances p1, p2. For uniform ventilation in the anodizing bath, the distances r1, r2 are preferably 100 to 120 mm and the distances p1, p2 are at least 50 mm.

In the block diagram in 20 For example, (A), (C), and (D) are the aforementioned vibrating stirring device, the vibration transmitting device, and (B) 'is the above-mentioned manifold. A suitable voltage is applied via the regulator, which is required for the anodization process between the object to be treated or the anode and the cathode. The anodizing bath in the anodizing tank 1 is circulated by means of a pump via a heat exchanger. The air blower supplies compressed air to the distributor pipe (B) '. The ventilation device (B) includes the manifold (B) 'and the blower.

The present invention can be implemented without operating at least one of the devices (C) and (D). In other words, at least one of the devices (C) and (D) can be used in the same manner as in the above-mentioned 1 to 3 shown embodiment are omitted.

21 Fig. 10 is a diagram showing an example of the course of the initial current density during the anodization process under gentle conditions. The current density is adjusted so that it increases gradually.

According to the present invention, an in 22 shown continuous and automated treatment system or a treatment line can be realized, wherein the metal body or the object to be treated is passed through treatment container for carrying out the above-mentioned processes of pretreatment, anodization and post-treatment.

In the treatment containers for the Pre-treatment process or the aftertreatment process is preferably the device (A) used, wherein a use of the devices (A) and (B) is even more preferable. Preference is also the Use of the combination of devices (A) + (B) + (C), the Devices (A) + (B) + (D) or devices (A) + (B) + (C) + (D).

These Devices) is (are) preferably in at least one of Steps of degreasing, polishing by the way of electrolytic or chemical polishing and densification by means of hot water used to increase the efficiency of the step in question.

For example, if the vibratory agitator (A) is operated during the electrolytic polishing operation, the following composition can be used for the treatment bath: H ₃ PO ₄ (89% aqueous solution) 300 g / liter H ₂ PO ₄ 200 g / liter glycerin 10 g / liter

The Concentration of this composition is relatively low, and the relatively low treatment temperature of 50 to 60 ° C and the relatively short treatment time of 7 to 11 minutes can be as a contribution to reduce costs. In addition, the obtained Anodically produced oxide film has a good appearance and appearance good gloss on.

To the contrary, the vibrationally (A) not used in the electrolytic polishing process, wherein a current density of 10 to 16 A / dm ^2, a voltage of 5 to 20 V and at a treatment temperature of 90 to 100 ° C, the relatively long treatment time of 10 to 15 minutes if the following composition is used for the treatment bath: H ₃ PO ₄ (89% aqueous solution) 600 g / liter H ₂ PO ₄ 400 g / liter glycerin 10 g / liter

The Concentration of this composition is relatively high.

Also in the case of the chemical polishing process, by using the vibrationally (A) the treatment temperature is lowered considerably, and the obtained anodic oxide film has a good external appearance and good shine.

in the The following are examples according to the invention and comparative examples, but is the general inventive idea not limited to the following examples.

In the following examples, the in 20 shown device used. However, in certain examples, the devices (C) and / or (D) are not operated as shown in FIG 1 to 3 ,

example 1

There was a device of the in the 1 to 3 used type shown. The size, performance, etc. of each constituent device were as follows:

(1) Anodizing tank

It became a container made of heat resistant Polyvinyl chloride with a width of 500 mm, a length of 750 mm and a height used by 550 mm.

(2) vibrating stirring device

• Schwingungsmotor: URAS VIBRATOR KEE 3.5–2B, erhältlich bei YASKAWA & CO., LTD., 250 W × 200 V × 3-phasig, gesteuert durch einen Wechselrichter (0,4 kW).
• Schwingblatt: 300 × 100 mm wirksame Fläche, 0,5 mm Dicke (es wurden fünf Blätter verwendet), α = 15 Grad (das unterste Blatt war nach unten geneigt, die übrigen Blätter waren nach oben geneigt)
• Amplitude eines Schwingblatts: 1,5 mm

It was manufactured by JAPAN TECHNO CO., LTD. prepared stirrer SUPERVIBRATING α AGITATOR Type 3 used.

• Vibration motor: URAS VIBRATOR KEE 3.5-2B, available from YASKAWA & CO., LTD., 250 W × 200 V × 3-phase, controlled by an inverter (0.4 kW).
• Oscillating blade: 300 × 100 mm effective area, 0.5 mm thick (five leaves were used), α = 15 degrees (the lowest leaf was tilted downwards, the remaining leaves were tilted upwards)
• Amplitude of an oscillating blade: 1.5 mm

(3) Manifold

• Innendurchmesser: 50 mm
• Außendurchmesser: 75 mm
• Länge: 450 mm
• Porosität: 33 bis 38 %
• Größe der Porenöffnungen: 50 bis 60 µm
• Volumendichte: 2,2 bis 2,5

It was manufactured by JAPAN TECHNO CO., LTD. manufactured aeration device MICRO AERATOR BM-100 made of ceramic used.

• Inner diameter: 50 mm
• Outer diameter: 75 mm
• Length: 450 mm
• Porosity: 33 to 38%
• Size of the pore openings: 50 to 60 μm
• Volume density: 2.2 to 2.5

(4) Blower for the manifold

A rotary air pump with 150 W was used.
Pumping capacity: 120 liters / min

(5) Anodizing bath

• Volume: 160 liters

(6) cathode

It Four aluminum plates were used, each one width of 60 mm, one length of 500 mm and a thickness of 20 mm.

(7) Subject to be treated (Metal body: Anode)

An aluminum plate of A1100P (JIS H400) having a width of 100 mm, a length of 100 mm and a thickness of 1.5 mm was used. Si + Fe ≤ 1.0% Cu = 0.05 - 0.20% Mn ≤ 0.05% Zn≤0.10% Al ≥ 99.0%

(8) Holder for treatment object

A titanium support frame and aluminum wires were used to attach the object to be treated to the support frame (see 17 ).

(9) Heat exchanger for cooling the treatment bath

It became one of SHOWA ENTETSU CO., LTD. made automatic, directly cooling Rapid cooling apparatus, used of the type COOL LINER. 4010 kcal / h, engine 1.5 kW

(10) Circulation pump for the heat exchanger

• Maximale Umwälzleistung: 120 Liter/Min
• Maximale Wasserdruckhöhe: 8,6 m
• Ausgang: 265 W, 1,27 A

A magnetic pump type IWAKI MD-100RM was used.

• Maximum circulation capacity: 120 liters / min
• Maximum water pressure level: 8.6 m
• Output: 265 W, 1.27 A

(11) controller

• Nennleistung: 60 V – 100 A, 6,0 kW
• Wechselstromeingang: 200 V; 21,2 A; 7,34 kVA

It was made by CHUO SEISAKUSHO CO., LTD. manufactured direct current source HIMINI MB7C-600-01 used.

• Rated power: 60 V - 100 A, 6,0 kW
• AC input: 200 V; 21.2 A; 7.34 kVA

(12) Distance between anode and cathode (d2, d3 in Fig.18)

• 100 mm

(13) Arrangement of treatment tanks

• Beizbehandlung: Bad mit Natronlauge 50 g/Liter,
• Behandlungsdauer 5 Minuten bei Raumtemperatur
• Dekapierbehandlung: Bad mit 5-prozentiger Salpetersäurelösung,
• Behandlungsdauer 1 Minute bei Raumtemperatur
• Verdichtungsbehandlung: mit lonenaustauscher behandeltes, abgekochtes Wasser,
• Behandlungsdauer 15 Minuten bei Raumtemperatur

Degreasing container → Container for cleaning with water → Pickling container → Container for cleaning with water → Discharge container → Container for cleaning with water Anodizing container → Container for cleaning with water → Compression container Dry container

• Pickling: Bath with sodium hydroxide 50 g / liter,
• Treatment time 5 minutes at room temperature
• Decorating treatment: bath with 5% nitric acid solution,
• Treatment time 1 minute at room temperature
• Compaction treatment: with ion exchanger treated, boiled water,
• Treatment time 15 minutes at room temperature

The anodization was carried out for 8 minutes, and the frequency of the vibration motor of the device (A) was 37 Hz to generate vibration of the vibration blade at a frequency of 600 cycles per minute. The anode potential was 20 V, the current density was in 21 shown and the temperature of the bath was 20 ° C.

On the surface of the object to be treated was formed anodically generated Oxide film with a thickness of 20 microns. The oxide film had a good density and a good appearance and shine on. The result is shown in Table 2.

Comparative Example 1

Of the Anodization procedure was as in Example 1, except that that the vibrating stirring device (A) was not operated. The treatment duration required was to form an anodically-generated oxide film of thickness 20 μm, i.e. the same thickness as in Example 1, was 40 minutes. The result is shown in Table 2.

Table 2

Evaluation:

The current density of 10 A / dm ² in Example 1 is considerably larger than the current density of 2 A / dm ² in Comparative Example 1. Accordingly, the anodization rate in Example 1 is about 5 times higher than Comparative Example 1. Hardness, corrosion resistance, coloring properties and Wear characteristics of the oxide film obtained in Example 1 are an improvement over Comparative Example 1.

in the Essentially resulted for Oxide films with a thickness of 10 microns or 15 microns same tendency.

Example 2

The anodizing operation was carried out in the same manner as in Example 1 except that the treatment time was 5 minutes with the vibration motor of the apparatus (A) operated at 150V The anode potential was 15V and the temperature of the bath was 30 ° C. The result is shown in Table 3.

Comparative Examples 2-1 and 2-2

The anodizing except in the same way as in Example 2, that the vibrating stirring device (A) was not operated. In Comparative Example 2-2 was the treatment duration chosen so that an oxide film of the same thickness as in Example 2 was formed. The result is shown in Table 3.

Table 3

Evaluation:

in the Example 2, the anodization rate was about 4 times higher than in the comparative example 2-2, and the oxide film has a good gloss and is more adequate quality for the practical use. In contrast, is the oxide film used in Comparative Examples 2-1 and 2-2 in a Bath temperature of 30 ° C obtained was of inadequate quality for the practical use.

Example 3

The anodization process was carried out in the same manner as in Example 1, except that the aluminum plate of the article to be treated was a hard aluminum plate of A5052P (JIS H400). Si ≤0.25% Fe ≤0.04% Cu = 0.01% Mn≤0.01% Mg = 2.2 - 2.8% Cr = 0.15 - 0.35% Zn ≤0.1% The result is shown in Table 4.

Comparative Example 3

Of the Anodization procedure was as in Example 3, except that that the vibrating stirring device (A) was not operated. The result is shown in Table 4.

Table 4

Evaluation:

in the Example 3, in which a hard anodic oxide film formed, the anodization rate is about 4 times higher than in Comparative Example 3. The external appearance, the Hardness, the corrosion resistance, the dyeing properties and the wear characteristics of the oxide film obtained in Example 3 are superior to that of Comparative Example 3 is an improvement.

Example 4

The anodizing processes were performed in the same manner as in Example 1 except that the aluminum plate of the above-mentioned material A5052P (JIS H400) was, the current density of 8 A / dm ² and the temperature at which the oxide films having a thickness of 15 microns formed, as in 23 (Symbols o) was varied. The hardness (Hv) of the oxide films was measured. The result is in 23 shown.

Comparative Example 4

The anodizing operations were carried out in the same manner as in Example 4, except that the vibrating agitator (A) was not operated, the current density was 1.5 A / dm ² , and the temperature of the anodizing bath was as in 23 (Symbols •) was varied. The hardness of the oxide films was measured. The result is in 23 shown.

Evaluation:

Of the The oxide film obtained in Example 4 has a higher hardness (Hv) than that in Comparative Example 4 oxide film obtained at the same bath temperature. To according to the present Invention to form an oxide film of the same hardness, so at a higher one Temperature to be worked than in the conventional method, and the The present invention thus relates to energy consumption and treatment time significant benefits.

Example 5

Of the Anodization process was carried out in the same manner as in Example 1, except that the object to be treated by a casting process manufactured aluminum body was, its distinctions about 150 mm × 120 mm × 40 mm and which had numerous depressions, the irregular on the surface a width of 3 to 15 mm and a depth of about 15 to 20 mm. An oxide film of thickness 15 μm was formed. The result is shown in Table 5.

Comparative Example 5

Of the Anodization process is done in the same way as in the example 5, except that the Schwingrührvorrichtung (A) not operated has been. The result is shown in Table 5.

Table 5

Evaluation:

Of the obtained in Example 5 oxide film is also in the wells of uniform thickness, during the obtained in Comparative Example 5 oxide film of uneven thickness is, i. the film formed in the wells is considerably thinner than the film made in other areas and its brilliance is opposite to the example 5 weaker, although the treatment time in Comparative Example 5 is about 4 times the treatment time in Example 5 was. Accordingly, it is possible the present invention in cases apply in which the object to be treated on its surface depressions each recess having a width of 10 mm and a depth from 10 to 15 mm.

Example 6

Of the Anodization process was carried out in the same manner as in Example 5, except that the temperature of the Anodisierbads 30 ° C and the Air pumping capacity was 240 liters / min. The treatment duration, the required to form a film of thickness 15 μm, was only 5 minutes.

Such An increased speed of the anodization process allows one Line, in the pre-treatment, anodizing and after-treatment continuously take place, wherein a conveying device the continuous transport of the object to be treated is used.

Comparative Example 6

Of the Anodization process was carried out in the same manner as in Example 6, except that the Schwingrührvorrichtung (A) not operated has been. The obtained oxide film was very irregular and irregular practically unusable.

Example 7-1

There was a device of the in the 13 to 15 used type shown. The size, power, etc. of each subcomponent were the following:

Arrangement of treatment tanks

Degreasing container (o) → container for cleaning with water → pickling tank → container for cleaning with Water → Discharge tank (o) → Container for cleaning with Water → Anodising tank (•) → Container for cleaning with water → compression tank (o) → drying tank

The Devices (A) to (D) were in the above designated i container used in combination, and the device (A) were in the used above with o designated containers. The treatment bath in the container for cleaning with water was tap water at room temperature.

Object to be treated (Metal body: Anode)

It was an aluminum plate with the dimensions 500 mm × 200 mm × 10 mm used.

cathode

It Eight aluminum plates were used, their dimensions each 500 mm × 60 mm × 20 mm.

The object to be treated and the cathode were analogous to those in 18 arranged situation shown. A set of four cathodes was arranged in a row on one side of the object to be treated at a distance d2 of 100 mm, the other set of four cathodes was arranged in a row on the other side of the object to be treated at a distance d3 of 100 mm arranged, and the distance d1 was 15 mm.

Anodizing

It became a container with a width of 500 mm, a length of 750 mm and a height of 550 mm used.

vibrationally

• Vibration motor: URAS VIBRATOR, 250 W × 200 V × 3-phase, controlled by means of of an inverter at an oscillation frequency of 37 Hz
• Vibration blade: 300 × 150 mm effective area, 0.6 mm thick (six vibration vanes were used), α = 15 degrees (the lowest swing leaf was down and the others swing leaves were tilted upwards)
• Amplitude of the vibration vanes: 1.5 mm
• Frequency of the vibration vanes: 600 vibrations per minute

aeration device

• Innendurchmesser: 50 mm
• Außendurchmesser: 75 mm
• Länge: 450 mm
• Porosität: 40 %
• Größe der Porenöffnungen: 200 µm

Three distribution tubes made of ceramic were used.

• Inner diameter: 50 mm
• Outer diameter: 75 mm
• Length: 450 mm
• Porosity: 40%
• Size of pore openings: 200 μm

When air blower for the Manifolds became a rotary air pump with a power used by 150 W and an air pumping capacity of 120 liters / min.

oscillating device

One Geared motor or cylinder engine was used to oscillate of the object to be treated in the direction along its surface a vibration amplitude of 40 mm and a frequency of 20 vibrations to produce per minute.

Vibration transmitting device

Of the Vibration motor 14 with a power of 40 W was on the vibrating Carrying frame mounted and over an inverter operated at a frequency of 30 Hz to the object to be treated in vibrations with a frequency of 250 vibrations per minute and an amplitude of 0.8 mm too offset.

anodizing

• Volume: 150 liters
• level: 400 mm above the bottom of the container

Heat exchanger for cooling the treatment bath

It was developed by SHOWA ENTETSU CO., LTD. manufactured cooling device NEW COOL LINER SA3-2 used.
4010kcal / h, engine 1.5 kW

Circulation pump for the heat exchanger

• Maximum circulation rate: 120 liters / min
• Output: 265 W, 1.27 A

• Entfettungsbad Es wurde eine Hydrogencarbonat-Entfettungsmittel von der Art eines Naphthenentfettungsmittel (TECHNO CLEAN S800) verwendet. Die Temperatur betrug 40 °C, und die Behandlungsdauer betrug 5 Minuten. Die Innenabmessungen des Entfettungsbehälters waren 500 mm Breite, 750 mm Länge und 550 mm Höhe.
• Beizbad Schwefelsäure (spezifisches Gewicht 1,84) 500 ml/Liter Phosphorsäure (spezifisches Gewicht 1,74) 100 ml/Liter Chromsäure 30 g/Liter Die Temperatur betrug 65 °C, und die Behandlungsdauer betrug 10 Minuten. Die Innenabmessungen des Beizbehälters waren 500 mm Breite, 750 mm Länge und 550 mm Höhe.
• Dekapierbad NO₃ 5-prozentige wässrige Lösung
• Verdichtungsbad Mit lonenaustauscher behandeltes, abgekochtes Wasser Das Ergebnis ist in Tabelle 6 gezeigt.

The process steps were the same as in Table 1 above, but the following special treatment baths were used with the respective treatment time indicated:

• Degreasing Bath A bicarbonate degreaser of the naphthene degreasing type (TECHNO CLEAN S800) was used. The temperature was 40 ° C and the treatment time was 5 minutes. The internal dimensions of the degreasing container were 500 mm wide, 750 mm long and 550 mm high.
• Pickling bath Sulfuric acid (specific gravity 1.84) 500 ml / liter Phosphoric acid (specific gravity 1.74) 100 ml / liter Chromic acid 30 g / liter The temperature was 65 ° C and the treatment time was 10 minutes. The internal dimensions of the pickling tank were 500 mm wide, 750 mm long and 550 mm high.
• Dekapierbad NO ₃ 5 percent aqueous solution
• Compression bath Boiled water treated with ion exchanger The result is shown in Table 6.

Example 7-2

Of the Anodization process was done in the same way as in Example 7-1, apart that the vibration transmission device (C) and the oscillating device (D) were not operated. The result is shown in Table 6.

Table 6

Example 8-1

There was a device of the in the 4 to 8th used type shown. The size, power, etc. of each subcomponent were the following:

Anodizing

It became a container width 500 mm, length 1250 mm and the height 750 mm used.

anodizing

Object to be treated (Metal body: Anode)

It was an aluminum plate with the dimensions 500 mm × 200 mm × 10 mm used.

cathode

It Ten aluminum plates were used, the dimensions of each 500 mm × 60 mm × 20 mm and in the vertical direction parallel to each other were arranged.

The object to be treated and the cathode were analogous to those in 18 arranged situation shown. A set of five cathodes was arranged in a row on one side of the object to be treated at a distance d2 of 100 mm, the other set of five cathodes was arranged in a row on the other side of the object to be treated at a distance d3 of 100 mm arranged, and the distance d1 was 15 mm. The uppermost area of the article to be treated was 70 mm below the surface of the treatment bath, and the lowest area of the article to be treated was 70 mm higher than the bottom of the treatment tank.

Vibratory stirring device (A)

• Vibration motor: URAS VIBRATOR, 400 W × 200 V × 3-phase, controlled by of an inverter at an oscillation frequency of 37 Hz
• Vibration blade: 300 × 150 mm effective area, 0.6 mm thick (eight vibration vanes were used), α = 15 degrees (the lowest swing leaf was down and the others swing leaves were tilted upwards)
• Amplitude of the vibration vanes: 1.5 mm
• Frequency of the vibration vanes: 600 vibrations per minute

It were two vibratory stirring devices (A) used.

Ventilation device (B)

• Innendurchmesser: 50 mm
• Außendurchmesser: 75 mm
• Länge 800 mm
• Porosität: 40
• Größe der Porenöffnungen: 200 µm

Three distribution tubes made of ceramic were used.

• Inner diameter: 50 mm
• Outer diameter: 75 mm
• Length 800 mm
• Porosity: 40
• Size of pore openings: 200 μm

It became an air blower used with an air pumping capacity of 200 liters / min.

Oscillating device (D)

One Geared motor or cylinder engine was used to oscillate of the object to be treated in the direction along its surface a vibration amplitude of 40 mm and a frequency of 20 vibrations to produce per minute.

Vibration transmitting device (C)

Of the Vibration motor 14 with a power of 40 W was on the vibrating Carrying frame mounted and over an inverter operated at a frequency of 30 Hz to the object to be treated in vibrations with a frequency of 250 vibrations per minute and an amplitude of 0.8 mm too offset.

Heat exchanger for cooling the treatment bath

A COOL LINER type quick cooling device was used for automatic, direct cooling.
4010kcal / h, engine 1.5 kW

Circulation pump for the heat exchanger

• Maximale Umwälzleistung: 120 Liter/Min
• Maximale Wasserdruckhöhe: 8,6 m
• Ausgang: 265 W, 1,27 A

A magnetic pump was used.

• Maximum circulation capacity: 120 liters / min
• Maximum water pressure level: 8.6 m
• Output: 265 W, 1.27 A

regulator

• Nennausgangsgrößen: 60 V – 100A, 6,0 kW
• Wechselstromeingang: 200 V; 21,2A; 7,34 kVA

A direct current source was used.

• Rated output: 60V - 100A, 6.0kW
• AC input: 200 V; 21,2A; 7.34 kVA

The Process steps were the same as in the above table 1, wherein the devices (A) to (D) in the steps for Degreasing and were used for compaction.

The Result is shown in Table 7.

Example 8-2

Of the Anodization process was carried out in the same manner as in Example 8-1, apart that the vibration transmission device (C) and the oscillating device (D) were not operated. The result is shown in Table 7.

Table 7

Example 9-1

The anodizing operation was carried out in the same manner as in Example 8-1, using a hard aluminum plate of the material A5052P (JIS H 400) as the object to be treated and the temperature of the anodizing bath 7 ° C, the current density 15 A / cm ² and treatment time was 10 minutes.

The thus treated aluminum plate was as in 24 are divided into 15 areas, and the thickness and hardness of the oxide film were measured at the center of each area, respectively. The measuring points are in 24 denoted by small circles o. The result is shown in Tables 8 and 9.

Table 8 (thickness, μm)

• Average thickness value: 44.7 μm
• Value of the minimum thickness: 44.1 μm
• Value of the maximum thickness: 45.2 μm

Table 9 (Hardness, Hv)

• Value of mean hardness: 518
• Value of the minimum hardness: 511
• Value of maximum hardness: 527

Example 9-2

Of the Anodization process was carried out in the same manner as in Example 9-1, apart that the vibration transmission device (C) and the oscillating device (D) were not operated. The result is shown in Tables 10 and 11.

Table 10 (thickness, μm)

• Average thickness value: 37.0 μm
• Value of the minimum thickness: 35.7 μm
• Value of the maximum thickness: 38.0 μm

Table 11 (Hardness, Hv)

• Value of mean hardness: 404
• Value of the minimum hardness: 397
• Value of maximum hardness: 415

Out a comparison of Tables 8 and 9 with Tables 10 and 11 It can be seen that the anodization process in which all devices (A) to (D) leads to a better result than the anodization process in which the devices (A) and (B), but not the devices (C) and (D) are operated. Actually points in Example 9-1 oxide film obtained in comparison with that obtained in Example 9-2 Oxide film one at about 20% greater thickness at higher uniformity and one at about 30 % higher Vickers hardness although the temperature of the anodizing bath and the treatment time in the two examples 9-1 and 9-2 they were the same.

If the anodizing process is carried out while the devices (A) to (C) are operated without the device (D) operated is, the value that the thickness of the obtained oxide film assumes is between the values of Examples 9-1 and 9-2, while the Vickers hardness of Oxide film assumes substantially the same value as in the example 9-1.

If the anodizing process is carried out while the devices (A), (B) and (D) is operated without the device (C) operated is, the value is the Vickers hardness of the obtained oxide film between the values of Examples 9-1 and 9-2, while the Thickness of the oxide film assumes substantially the same value as in Example 9-1.

It it has been found that the use of the device (D) advantageous in that they are the smoothness and uniformity the surface the oxide film in particular in the case of a plate-shaped to be treated Item improved.

Example 10

There was a device of the in the 1 to 3 used type shown. The size, power, etc. of each subcomponent were the following:

(1) Anodizing tank

It became a container made of heat resistant Polyvinyl chloride with a width of 700 mm. a length of 1000 mm and a height used by 700 mm.

(2) vibrating stirring device

• Schwingungsmotor: URAS VIBRATOR KEE 10–2B, 750W × 200 V × 3-phasig, gesteuert mittels eines Wechselrichters (1 kW)
• Schwingblatt: 300 × 150 mm wirksame Fläche, 0,6 mmDicke (es wurden sechs Schwingblätter verwendet), α = 15 Grad (das unterste Schwingblatt war nach unten geneigt und die anderen Schwingblätter waren nach oben geneigt)
• Amplitude der Schwingblätter: 1,5 mm
• Frequenz der Schwingblätter: 700 Schwingungen pro Minute

It was manufactured by JAPAN TECHNO CO., LTD. manufactured SUPERVIBRATING AGITATOR type 5 used.

• Vibration motor: URAS VIBRATOR KEE 10-2B, 750W × 200 V × 3-phase, controlled by means of an inverter (1 kW)
• Oscillating blade: 300 × 150 mm effective area, 0.6 mm thick (six vibration vanes were used), α = 15 degrees (the lowest vibration blade was tilted down and the other vibration vanes were tilted upwards)
• Amplitude of the vibration vanes: 1.5 mm
• Frequency of vibrating blades: 700 vibrations per minute

(3) Manifold

• Innendurchmesser: 50 mm
• Außendurchmesser: 75 mm
• Länge 700 mm
• Porosität: 33 bis 38 %
• Größe der Porenöffnungen: 50 bis 60 µm
• Volumendichte: 2,2 bis 2,5

It was made by JAPAN TECHNO CO., LTD. manufactured model MICRO AERATOR BM-100 used in ceramic. Three distribution pipes were used.

• Inner diameter: 50 mm
• Outer diameter: 75 mm
• Length 700 mm
• Porosity: 33 to 38%
• Size of the pore openings: 50 to 60 μm
• Volume density: 2.2 to 2.5

(4) Air blower for the distribution pipes

It a rotary air pump with a power of 150 W was used. Air pumping capacity: 120 liters / min

(5) Anodizing bath

• Volume: 420 liters

(6) cathode

It ten aluminum plates were used.

(7) Subject to be treated (Metal body: Anode)

It was an aluminum body produced by casting, and Although a car part with dimensions of 250 mm × 750 mm × 500 mm and with numerous Depressions on the surface used.

(8) Heat exchanger for cooling the treatment bath

A COOL LINER type cooler was used.
4010kcal / h, engine 1.5 kW

(9) Circulation pump for the heat exchanger

• Maximale Umwälzleistung: 120 Liter/Min
• Maximale Wasserdruckhöhe: 8,6 m
• Ausgang: 265 W, 1,27 A

The magnetic pump IWAKI MD-100RM was used.

• Maximum circulation capacity: 120 liters / min
• Maximum water pressure level: 8.6 m
• Output: 265 W, 1.27 A

(10) controller

• Nennausgangsgrößen: 60 V – 100 A, 6,0 kW
• Wechselstromeingang: 200 V; 21,2 A; 7,34 kVA

It was manufactured by CHUO EISAKUSHP CO., LTD. manufactured DC power source HIMINI MB7C-600-01 used.

• Rated output sizes: 60 V - 100 A, 6.0 kW
• AC input: 200 V; 21.2 A; 7.34 kVA

(11) Distance between anode and cathode (d2, d3 in 18 )

100 mm

(12) Arrangement of treatment tanks

• Beizbehandlung: Bad in Natronlauge mit 50 g/Liter NaOH, Behandlungsdauer 5 Minuten bei Raumtemperatur
• Dekapierbehandlung: Bad in 5-prozentiger Salpetersäure, Behandlungsdauer 1 Minute bei Raumtemperatur
• Verdichtungsbehandlung: Bad in abgekochtem, mit lonenaustauscher behandeltem Wasser, Behandlungsdauer 30 Minuten bei Raumtemperatur
• Stromdichte: 5 A/dm²

Degreasing container → container for cleaning with water → pickling container → container for cleaning with water → picking container → container for cleaning with water Anodizing container → container for cleaning with water → compression container (o) Dry container

• Pickling treatment: bath in sodium hydroxide solution with 50 g / l NaOH, treatment time 5 minutes at room temperature
• Pickling treatment: bath in 5% nitric acid, treatment time 1 minute at room temperature
• Densification Treatment: Bath in boiled, ion-exchanged water, treatment time 30 minutes at room temperature
• Current density: 5 A / dm ²

The Anodizing treatment was over 8 minutes, wherein the frequency of the vibration motor of the device (A) 40 Hz, the bath temperature 30 ° C and the air pumping power was 120 liters / min.

On the surface of the object to be treated was formed anodically generated Oxide film with a thickness of 20 microns. The thickness of the oxide film was of good uniformity.

If the anodizing process is performed without the vibrating stirring device (A) is operated, it comes to the burning of the oxide film, and a Good anodically generated oxide film can not be obtained.

Example 11

Of the Anodization process was carried out in the same manner as in Example 10, except for the following:

• (1) The dimensions of the article to be treated were 100 mm × 500 mm × 300 mm.
• (2) The method described by JAPAN TECHNO CO., LTD. manufactured MICRO AERATOR B-100 off Ceramic used. Three distribution pipes were used. Inner Diameter: 50 mm Outer diameter: 70 mm Length: 500 mm Porosity: 33 to 38% Size of pore openings: 50 to 60 μm

The Anodizing treatment was over 5 minutes with a bath temperature of 30 ° C and an air pumping rate of 120 liters / min.

On the surface of the object to be treated was formed anodically generated Oxide film with a thickness of 15 microns. The thickness of the oxide film even in the wells was of good uniformity.

If the anodizing process takes place without the vibrating stirring device (A) is operated an air pumping capacity of more than 60 liters / min to ensure uniformity the thickness of the oxide film is lost, and thus an air pumping performance of more than 60 liters / min in practice will not be used. Will continue to be a higher Current density used, there is a tendency to burn the Oxide film, and therefore leaves the current density does not increase to the extent that a sufficient Anodization rate is obtained.

Claims (23)

A method of anodizing a metal body comprising an anodization process in which an anodically-generated oxide film is formed on the surface of the metal body immersed in an anodizing bath, the anodization process taking place during (a) the anodizing bath is agitated by a vibrating agitator, the anodising bath being agitated by a rocking agitator by vibrating a vibrating blade having an amplitude of 0.5 to 3.0 mm and a frequency of 200 to 800 vibrations per minute; and simultaneously (b) aeration in the anodizing bath using air bubbles producing a diffuser having a pore opening of 10 to 400 μm and a porosity of 30 to 40%. Anodization process according to claim 1, wherein the anodization process takes place while simultaneously (c) transmit a vibration to the metal body being, the metal body with an amplitude of 0.5 to 1.0 mm and a frequency of 100 is oscillated to 300 vibrations per minute. Anodization process according to claim 1, wherein the anodization process takes place while simultaneously (d) the metal body performs a swinging movement, being the body in a swinging motion with an amplitude of 10 to 100 mm and an oscillation frequency of 10 to 30 oscillations per minute is added. Anodization process according to claim 1, wherein the anodization process takes place while simultaneously (c) transmit a vibration to the metal body being, the metal body with an amplitude of 0.5 to 1.0 mm and a frequency of 100 is oscillated to 300 vibrations per minute, and simultaneously (D) the metal body performs a swinging movement, being the body in a swinging motion with an amplitude of 10 to 100 mm and an oscillation frequency of 10 to 30 oscillations per minute is added. A method of anodizing a metal body comprising an anodization process in which on the surface of the anodized metal body immersed in an anodizing bath Oxide film is formed, wherein the anodization process takes place, while simultaneously the following devices (A) and (B) are operated: (A) vibrationally for the Anodizing bath comprising a vibration generating agent containing a Vibration motor, a vibrating stirring means, around a vibration blade with an amplitude of 0.5 to 3.0 mm and a Oscillation frequency of 200 to 800 vibrations per minute in vibrations to create a vibrational flow in the anodizing bath, wherein the oscillating blade in one or more stages on a vibrating Rod is attached, which in conjunction with the vibration-generating Agent oscillates in the anodizing bath, and a means for catching the vibration stress at a junction of the vibration generating Means and the vibratory stirring means; and (B) Ventilation device for the Anodizing bath, which comprises a ceramic distribution tube, which has a Pore size of 10 up to 400 μm and a porosity from 30 to 40%. Anodization method according to claim 5, wherein the device (A) further comprises an inverter for controlling the vibration motor the device (A) to any frequency in the range of 10 to produce up to 500 Hz. Anodization method according to claim 5, wherein the anodization process takes place while simultaneously the following device (C) is operated: (C) device, around on the metal body over one Electrode rod on which the metal body is suspended, with a vibration an amplitude of 0.5 to 1.0 mm and a frequency of 100 to 300 vibrations per minute to transfer. Anodization method according to claim 7, wherein the device (C) by means of a vibration motor whose frequency by means of a Inverter is set to 10 to 60 Hz, one oscillation transfers to the metal body. Anodization method according to claim 5, wherein the anodization process takes place while simultaneously the following device (D) is operated: (D) device, to vibrate on an electrode rod to which the metal body is to be suspended transferred to, whereby the metal body mediated by the electrode rod performs a swinging motion with an amplitude of 10 to 100 mm and a frequency of 10 to 30 vibrations per minute. Anodization method according to claim 5, wherein the anodization process takes place while simultaneously the following devices (C) and (D) are operated: (C) Device to put on the metal body over a Electrode rod on which the metal body is suspended, with a vibration an amplitude of 0.5 to 1.0 mm and a frequency of 100 to To transmit 300 vibrations per minute; and (D) Device for applying to an electrode rod on which the metal body suspended is to be transmitted, a swinging movement, whereby the metal body mediates by the electrode rod performs a swinging motion with an amplitude of 10 to 100 mm and a frequency of 10 to 30 vibrations per minute. Anodization method according to one of claims 5 to 10, wherein the method takes place before the anodization process Pre-treatment process and / or after the anodization process comprising a subsequent aftertreatment process, and wherein at least a step in the pretreatment process or in the post-treatment process is included while operating the device (A). Anodizing method according to claim 11, wherein said one Minimum step takes place while simultaneously the device (B) is operated. Anodization method according to claim 12, wherein said one Minimum step takes place while simultaneously operated at least one of the devices (C) and (D) becomes. Anodizing method according to claim 11, wherein said one Minimum step a degreasing step, a polishing step with electrolytic or chemical polishing or a hot water sealing step is. Anodization method according to claim 12, wherein said one Minimum step a degreasing step, a polishing step with electrolytic or chemical polishing or a hot water sealing step is. Anodization method according to claim 13, wherein the one Minimum step a degreasing step, a polishing step with electrolytic or chemical polishing or a hot water sealing step is. Anodization method according to one of claims 1 to 10, wherein the metal body a blind hole with a diameter of at most 10 mm or a continuous one Hole with a diameter of at most 10 mm. Anodizing device for a metal body for execution anodization process in which on the surface of the anodized metal body immersed in an anodizing bath Oxide film is formed, comprising the following devices (A) and (B): (A) Vibratory stirring device for the Anodizing bath comprising a vibration generating agent containing a Vibration motor, a vibrating stirring means, around a vibration blade with an amplitude of 0.5 to 3.0 mm and a Oscillation frequency of 200 to 800 vibrations per minute in vibrations to create a vibrational flow in the anodizing bath, wherein the oscillating blade in one or more stages on a vibrating Rod is attached, which in conjunction with the vibration-generating Agent oscillates in the anodizing bath, and a means for catching the vibration stress at a junction of the vibration generating Means and the vibratory stirring means; and (B) Ventilation device for the Anodizing bath, which comprises a ceramic distribution tube, which has a Pore size of 10 up to 400 μm and a porosity from 30 to 40. Anodizing device according to claim 18, wherein the device (A) further comprises an inverter for controlling the vibration motor the device (A) to any frequency in the range of 10 to produce up to 500 Hz. Anodizing apparatus according to claim 18 further comprising the following device (C): (C) Device to contact the metal body via a Electrode rod on which the metal body is suspended, with a vibration an amplitude of 0.5 to 1.0 mm and a frequency of 100 to 300 vibrations per minute to transfer. Anodizing device according to claim 20, wherein the device (C) by means of a vibration motor whose frequency by means of a Inverter is set to 10 to 60 Hz, one oscillation transfers to the metal body. Anodizing apparatus according to claim 18 further comprising the following device (D): (D) device to turn on one Electrode rod on which the metal body is to be suspended, a swinging motion transferred to, whereby the metal body mediated by the electrode rod performs a swinging motion with an amplitude of 10 to 100 mm and a frequency of 10 to 30 vibrations per minute. Anodizing apparatus according to claim 18 further comprising the following devices (C) and (D): (C) device to on the metal body over one Electrode rod on which the metal body is suspended to transmit a vibration with an amplitude of 0.5 to 1.0 mm and a frequency of 100 up to 300 vibrations per minute; and (D) device to turn on an electrode rod on which the metal body is to be suspended, a swinging motion transferred to, whereby the metal body mediated by the electrode rod performs a swinging motion with an amplitude of 10 to 100 mm and a frequency of 10 to 30 vibrations per minute.