EP2729604B1 - Method for producing a bonding layer on a surface of a titanium workpiece - Google Patents

Method for producing a bonding layer on a surface of a titanium workpiece Download PDF

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EP2729604B1
EP2729604B1 EP12791239.2A EP12791239A EP2729604B1 EP 2729604 B1 EP2729604 B1 EP 2729604B1 EP 12791239 A EP12791239 A EP 12791239A EP 2729604 B1 EP2729604 B1 EP 2729604B1
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range
concentration
specifically
adhesion
titanium material
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German (de)
French (fr)
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EP2729604A2 (en
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Tobias Mertens
Franz Gammel
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Airbus Defence and Space GmbH
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Airbus Defence and Space GmbH
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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
    • C25D11/26—Anodisation of refractory metals or alloys based thereon

Definitions

  • the invention relates to a method for producing an adhesion-promoting layer on a surface of a titanium material, to a process-promoting adhesion-promoting layer on the surface of the titanium material and to the use of an alkaline solution.
  • adhesion-promoting layers on a surface of a titanium material is known.
  • organic materials such as, for example, adhesive, lacquer, sealant and / or the like can be bonded to the titanium material.
  • the adhesion-promoting layer on the surface of the titanium material can be produced, for example, by means of an anodic oxidation, that is, for example, consist of an oxide layer. This oxide layer may be used as the primer layer for subsequent coating of the titanium material with the organic material.
  • the US 4,473,446 discloses a method of surface treating titanium parts prior to bonding by anodizing in a chromic hydrofluoric acid bath at an anodization voltage between one volt and 5 volts.
  • the US 4,394,224 discloses a method of treating titanium parts or titanium alloy parts to produce an adhesion promoting oxide layer. It is the steps of applying to the surface and treating the surface with a mixture of aqueous solutions of sodium hydroxide and hydrogen peroxide, maintaining the applied mixture within a temperature range in which the hydrogen peroxide is relatively stable and causing an increased oxidation rate on the surface area.
  • the DE 34 27 543 A1 refers to an alkaline bath for treating titanium. The bath consists of an alkali hydroxide, a titanium complexing agent and an impurity complexing agent.
  • the US 3,907,609 discloses a chemical conversion process and composition for producing an adhesive conversion coating on titanium and titanium alloys.
  • 6,037,060 relate to a surface treatment, preferably for titanium and aluminum alloys, for forming a sol-gel film adhered to the metal surface by means of covalent bonds, for producing a strong and durable adhesive bond between the metal and an organic adhesive without the use of toxic chemicals and significantly reducing and / or eliminating rinse water requirements of conventional anodization and / or etching processes.
  • the DE 38 02 043 C1 relates to a method of preparing a metal surface.
  • amorphous silicon-containing material having a particle size less than 1 micron and the remainder of a sandblasting medium having an average particle size greater than 1 micron applied a layer and then optionally silanized.
  • the DE 10 2006 045 951 A1 relates to a process for the chemical modification and / or activation of solid surfaces.
  • the object of the invention is to provide an alternative method for producing an adhesion-promoting layer on a surface of a titanium material, for the implementation of which only or at least predominantly environmentally friendly chemicals are needed.
  • the object is achieved by a method according to claim 1.
  • the method for producing an adhesion-promoting layer on a surface of a titanium material comprises introducing the surface into an aqueous alkaline solution comprising sodium hydroxide having a concentration in a range of 100-300 g / l, Sodium tartrate having a concentration in a range of 20-200 g / l, methylglycinediacetic acid Na3 having a concentration in a range of 5 g / l - 60 g / l, pentasodium triphosphate having a concentration in a range of 2 g / l - 20 g / l, and applying a voltage between solution and titanium material for a predetermined period of time to produce the layer by anodic oxidation of the surface.
  • Sodium hydroxide is preferably in the range of 150-285 g / l, more preferably 175-270 g / l, 195-250 g / l, 210-240 g / l, 238-242 g / l, and especially of 240 g / l before.
  • Sodium tartrate is preferably at a concentration in a range of 20-200 g / l, more preferably 60-140 g / l, 75-125 g / l, 85-110 g / l, 90-105 g / l, especially of 100 g / l before.
  • Methylglycinediacetic acid Na3 is preferably present at a concentration in the range of 10-50 g / l, more preferably 15-40 g / l, 20-35 g / l, 25-33 g / l, 28-32 g / l, especially of 30 g / l before.
  • Pentasodium triphosphate is preferably present at a concentration of 3-17 g / l, more preferably 4.5-13 g / l, or 6-10 g / l, or 7-8 g / l, especially 7.5 g / l ,
  • Each of the above concentration ranges or concentrations of one of the constituents of the solution may be combined with any concentration range or concentration of any other constituent.
  • an adhesion-promoting layer in the form of an oxide layer can be provided on the surface of the titanium material, which has at least as good adhesion-promoting properties as in the prior art.
  • Sodium hydroxide contains Na + ions, which are known from conventional saline.
  • Pentasodium triphosphate also known as triphosphate, is a component of biological compounds such as adenosine triphosphate.
  • pentasodium triphosphate is approved as a food additive, so compared to chemicals used in the prior art is a particularly harmless substance.
  • Methylglycinediacetic acid Na 3 also known as the sodium salt of methylglycinediacetic acid, is used in particular as a cleaning agent, in particular as a dishwashing detergent, and is insofar harmless from an environmental point of view.
  • Methylglycinediacetic acid is also known as MGDA.
  • Sodium tartrate is a sodium salt of tartaric acid, also approved as a food additive and therefore also particularly harmless from an environmental point of view. The sodium tartrate acts as a titanium complexing agent in the alkaline solution and can thus advantageously improve the return properties.
  • Methylglycinediacetic acid Na 3 acts as a foreign ion complexing agent and pentasodium triphosphate as a scaffolding agent.
  • the alkaline solution is completely fluoride-free and yet allows optimum pretreatment of the surface of the titanium material for long-term stable, high-strength bonds of organic coatings.
  • a titanium material may be understood to be pure titanium or a titanium alloy, for example a titanium alloy with the designation Ti6Al4V.
  • the anodization is advantageously carried out with a voltage in a range of 2 to 50 V, preferably 3 to 45 V, 5 to 35 V, 7 to 25 V, 9 to 20 V, 9 to 15 V, 10 - 12 V, specially made by 10 V.
  • the advantageous oxide layer can be produced.
  • the anodic oxidation of the surface is advantageously carried out for a period of time in which the advantageous adhesion-promoting layer can be produced on the surface of the titanium material.
  • the period of time is in a range of 5 to 60 minutes, preferably 8 to 50 minutes, 11 to 40 minutes, 15 to 30 minutes, 18 to 25 minutes, 19 to 22 minutes, especially 20 minutes.
  • the anodic oxidation is advantageously provided at a maximum current density at which the advantageous adhesion-promoting layer can be produced on the surface of the titanium material.
  • the maximum current density is in a range of 0.2 - 10 A / dm 2 , preferably 0.4 - 8 A / dm 2 , 0.6 - 4 A / dm 2 , 0.8 - 2 A / dm 2 , 1 , 0-1.5 A / dm 2 , 1.1-1.3 A / dm 2 , especially of 1.2 A / dm 2 .
  • the anodization is advantageous at a temperature at which the advantageous adhesion-promoting layer can be produced on the surface of the titanium material.
  • the temperature is in a range of 5 to 60 ° C, preferably 10 to 50 ° C, 15 to 40 ° C, 20 to 35 ° C, 25 to 33 ° C, 28 to 32 ° C, especially 30 ° C.
  • anodic oxidation of the surface of the alkaline solution and thereby the production of an oxide layer of the layer thickness in a range of 50-600 nm, preferably 70-400 nm, 100-250 nm, especially of 150 nm is provided.
  • a particularly good adhesion promotion can be generated at the specified layer thickness.
  • the object is also achieved by an adhesion-promoting layer on a surface of a titanium material, produced or prepared according to a previously described Method solved according to claim 11.
  • the surface of the titanium material has in particular a porous nanostructure with juxtaposed elevations with undercuts and in particular an interference coloring on.
  • the individual structures are on the order of 50-300 nm.
  • the adhesion-promoting layer on the surface of the titanium material can be coated and / or provided with organic material with long-term stability and with particularly good adhesive properties.
  • it can be recognized by means of interference coloring that the desired adhesion-promoting layer is actually present on the surface of the titanium material or that the titanium material has the adhesion-promoting layer on its surface.
  • FIG. 1 1 shows a schematic view of a device 1 for producing an adhesion-promoting layer on a surface 3 of a titanium material 5.
  • the device 1 has a bath 7 with an electrolyte 9.
  • the electrolyte 9 comprises sodium hydroxide, sodium tartrate, methylglycinediacetic acid-Na 3 and pentasodium triphosphate in an aqueous solution.
  • oxide layer of the titanium material 5 and the bath 7 are connected to an electrical energy source 11, wherein via the electrolyte 9 of the bath 7, a circuit is closed.
  • the electrical energy source 11 supplies a voltage 13, which causes a current 15 in the closed circuit via the electrolyte 9.
  • control and / or regulating devices for adjusting the voltage 13 and / or the current 15 may be provided.
  • the device 1 can by anodizing an in the Figures 2 and 3 shown oxide layer 17 are generated on the surface 3 of the titanium material 5.
  • Standards are in the Figures 2 and 3 each with a line, which are labeled with a length in nm, drawn.
  • the adhesion-promoting layer is produced on the surface 3 of the titanium material 5.
  • the surface 3 is first introduced into the alkaline solution or the electrolyte 9 containing bath 7, for example, by at least partial immersion of the titanium material 5 in the electrolyte 9.
  • the voltage 13 between the electrolyte 9 and the Titanium material 5 for a predetermined period of time for the preparation of the layer by anodic oxidation of the surface 3 of the titanium material 5 produced.
  • FIG. 2 shows a thirst for the surface 3 of the titanium material. 5
  • FIG. 3 shows a cryogenic fracture of the titanium material 5 together with the surface 3, wherein the oxide layer 17 can be seen.
  • a thickness of the oxide layer 17 symbolizes, which is about 150 nm.
  • the oxide layer 17 has a pronounced microporous nanostructure, with these bulbous outgrowths arranged side by side.
  • the bulbous outgrowths have a dimension of less than 300 nm, in particular less than 250 nm, in particular less than 200 nm, in particular less than 150 nm, preferably less than 50 nm to 100 nm, and form an advantageous microporous surface.
  • the surface 3 of the titanium material 5 is at least partially introduced into the bath 7, in particular immersed.
  • the voltage 13 is applied by 10 V by means of the electric power source 11.
  • the current 15 is adjusted so that a current density of at most 1.2 A / dm 2 occurs on the surface 3 of the titanium material 5.
  • the voltage 13 and the current 15 and thus the current density of 1.2 A / dm 2 are maintained for a period of 20 minutes.
  • the bath 7 is heated to a temperature of 30 ° C.
  • a heater and / or cooling can be provided.
  • the desired nanostructured surface 3, ie the oxide layer 17, can be achieved in a completely fluoride-free process for the pretreatment of the titanium material 5 in order to achieve long-term stable, high-strength bonds of organic coatings.
  • the described porous surface morphology can be produced on the titanium material 5.
  • This can be adherent coated, for example with organic materials such as adhesive, paint, sealant and / or the like.
  • the electrolyte 9 is not only fluoride-free, but contains exclusively or at least predominantly environmentally friendly ingredients that are particularly biodegradable.
  • the interference coloring can serve as proof of the treatment carried out and / or as an identification feature for corresponding treated components made of the titanium material 5.
  • the oxide layer 17 on the surface 3 of the titanium material 5 can also be used for bonding biological material, for example on implants.
  • the solution has at least in traces and / or as at least partial replacement of existing ions further constituents, in particular ions of the same period of a periodic table.

Description

Die Erfindung betrifft ein Verfahren zur Herstellung einer haftvermittelnden Schicht auf einer Oberfläche eines Titanwerkstoffs, eine verfahrensgemäße haftvermittelnde Schicht auf der Oberfläche des Titanwerkstoffs sowie eine Verwendung einer alkalischen Lösung.The invention relates to a method for producing an adhesion-promoting layer on a surface of a titanium material, to a process-promoting adhesion-promoting layer on the surface of the titanium material and to the use of an alkaline solution.

Das Herstellen von haftvermittelnden Schichten auf einer Oberfläche eines Titanwerkstoffs ist bekannt. Mittels der haftvermittelnden Schicht können organische Materialien wie beispielsweise Klebstoff, Lack, Dichtmittel und/oder Ähnliches mit dem Titanwerkstoff verbunden werden. Die haftvermittelnde Schicht auf der Oberfläche des Titanwerkstoffs kann beispielsweise mittels eines anodischen Oxidierens hergestellt werden, also beispielsweise aus einer Oxidschicht bestehen. Diese Oxidschicht kann als die Haftvermittlungsschicht für eine nachfolgende Beschichtung des Titanwerkstoffs mit dem organischen Material verwendet werden. Die US 4 473 446 offenbart ein Verfahren zum Oberflächen behandeln von Titanteilen vor einem Verkleben mittels Anodisieren in einem Chromflusssäurebad bei einer Anodisierspannung zwischen einem Volt und 5 Volt. Die US 4 394 224 offenbart eine Methode zum Behandeln von Titanteilen oder Titanlegierungsteilen zum Erzeugen einer haftvermittelnden Oxidschicht. Es sind die Schritte Auftragen auf die Oberfläche und Behandeln der Oberfläche mit einer Mischung von wässrigen Lösungen aus Natriumhydroxid und Wasserstoffperoxid, Halten der aufgetragenen Mischung innerhalb eines Temperaturbereiches in dem das Wasserstoffperoxid relativ stabil ist und bewirken einer erhöhten Oxidationsrate auf dem Oberflächenbereich. Die DE 34 27 543 A1 bezieht sich auf ein alkalisches Bad zum Behandeln von Titan. Das Bad besteht aus einem Alkalihydroxid, einem Titankomplexbildner und einem Fremdionenkomplexbildner. Die US 3 907 609 offenbart einen chemischen Konversionsprozess und eine Zusammensetzung zum Produzieren einer haftenden Konversionsbeschichtung auf Titan und Titanlegierungen. Die US 5 814 137 sowie die US 6 037 060 betreffen eine Oberflächenbehandlung, vorzugsweise für Titan- und Aluminiumlegierungen, zum Ausbilden eines Sol-Gel-Films, der mittels kovalenten Bindungen an der Metalloberfläche haftet, zum Erzeugen einer starken, und langlebigen Klebeverbindung zwischen dem Metall und einem organischen Klebstoff ohne Verwendung von giftigen Chemikalien und unter signifikanten Reduzierung und/oder Eliminierung von Spülwassererfordernissen von herkömmlichen Anodisierungs- und/oder Ätzprozessen. Die DE 38 02 043 C1 betrifft ein Verfahren zur Vorbereitung einer Metalloberfläche. Dazu wird für die Verbindung mit Kunststoff auf eine Metalloberfläche durch Sandstrahlen mit einem Mittel aus 0,1 bis 30 Gewichtsprozent gegebenenfalls silanisiertem, amorphen siliziumhaltigen Material mit einer Korngröße kleiner 1 µm und zum Rest aus einem Sandstrahlmedium mit einer mittleren Korngröße größer 1 µm eine Schicht aufgebracht und diese gegebenenfalls anschließend silanisiert. Die DE 10 2006 045 951 A1 betrifft ein Verfahren zur chemischen Modifizierung und/oder Aktivierung von Festkörperoberflächen. Es wird bei dem Verfahren unter Verwendung von mindestens einem Trägermedium, das der Energiezufuhr in die Oberfläche hinein dient und der Oberfläche eine oder mehrere halogenhaltige Verbindungen zuführt, die Zuführung der halogenhaltigen Verbindungen erfolgt unter gleichzeitigem Zusatz von siliziumorganischen Verbindungen oder Silanen oder metallorganischen Verbindungen oder Siliziumhydriden oder Metallhydriden in das Trägermaterial. Eine Anmeldung derselben Anmelderin mit dem amtlichen Aktenzeichen 10 2010 054 473.6 betrifft ein Verfahren zum Haftvermitteln einer Fläche eines Titanwerkstoffs, wobei das Verfahren Erzeugen einer mit der Fläche des Titanwerkstoffs fest verbundenen und Titandioxid (TiO2) aufweisende Nanotubes aufweisenden Haftvermittlungsschicht auf der Fläche und Haftfestes Aufbringen eines organischen Werkstoffs auf die die Nanotubes aufweisende Haftvermittlungsschicht aufweist.The production of adhesion-promoting layers on a surface of a titanium material is known. By means of the adhesion-promoting layer, organic materials such as, for example, adhesive, lacquer, sealant and / or the like can be bonded to the titanium material. The adhesion-promoting layer on the surface of the titanium material can be produced, for example, by means of an anodic oxidation, that is, for example, consist of an oxide layer. This oxide layer may be used as the primer layer for subsequent coating of the titanium material with the organic material. The US 4,473,446 discloses a method of surface treating titanium parts prior to bonding by anodizing in a chromic hydrofluoric acid bath at an anodization voltage between one volt and 5 volts. The US 4,394,224 discloses a method of treating titanium parts or titanium alloy parts to produce an adhesion promoting oxide layer. It is the steps of applying to the surface and treating the surface with a mixture of aqueous solutions of sodium hydroxide and hydrogen peroxide, maintaining the applied mixture within a temperature range in which the hydrogen peroxide is relatively stable and causing an increased oxidation rate on the surface area. The DE 34 27 543 A1 refers to an alkaline bath for treating titanium. The bath consists of an alkali hydroxide, a titanium complexing agent and an impurity complexing agent. The US 3,907,609 discloses a chemical conversion process and composition for producing an adhesive conversion coating on titanium and titanium alloys. The US 5,814,137 as well as the US Pat. No. 6,037,060 relate to a surface treatment, preferably for titanium and aluminum alloys, for forming a sol-gel film adhered to the metal surface by means of covalent bonds, for producing a strong and durable adhesive bond between the metal and an organic adhesive without the use of toxic chemicals and significantly reducing and / or eliminating rinse water requirements of conventional anodization and / or etching processes. The DE 38 02 043 C1 relates to a method of preparing a metal surface. For this purpose, for the connection with plastic on a metal surface by sandblasting with a means of 0.1 to 30 weight percent optionally silanized, amorphous silicon-containing material having a particle size less than 1 micron and the remainder of a sandblasting medium having an average particle size greater than 1 micron applied a layer and then optionally silanized. The DE 10 2006 045 951 A1 relates to a process for the chemical modification and / or activation of solid surfaces. It is in the process using at least one carrier medium, which serves the energy supply into the surface and the surface one or more halogen-containing compounds, the supply of the halogen-containing compounds takes place with simultaneous addition of organosilicon compounds or silanes or organometallic compounds or silicon hydrides or Metal hydrides in the carrier material. An application of the same applicant with the official file reference 10 2010 054 473.6 relates to a method for adhesion-promoting a surface of a titanium material, the method producing an adhesion-promoting layer firmly bonded to the surface of the titanium material and having titanium dioxide (TiO 2 ) having nanotubes and adhesion-resistant application an organic material having on the nanotubes having adhesion promoting layer.

Aufgabe der Erfindung ist es, ein alternatives Verfahren zur Herstellung einer haftvermittelnden Schicht auf einer Oberfläche eines Titanwerkstoffs bereit zu stellen, für dessen Durchführung ausschließlich oder zumindest überwiegend umweltfreundliche Chemikalien benötigt werden.The object of the invention is to provide an alternative method for producing an adhesion-promoting layer on a surface of a titanium material, for the implementation of which only or at least predominantly environmentally friendly chemicals are needed.

Die Aufgabe ist gelöst durch ein Verfahren gemäß Anspruch 1. Das Verfahren zur Herstellung einer haftvermittelnden Schicht auf einer Oberfläche eines Titanwerkstoffs, umfasst das Einbringen der Oberfläche in eine wässrige alkalische Lösung umfassend Natriumhydroxid mit einer Konzentration in einem Bereich von 100 - 300 g/l, Natriumtartrat mit einer Konzentration in einem Bereich von 20 - 200 g/l, Methylglycindiessigsäure-Na3 mit einer Konzentration in einem Bereich von 5 g/l - 60 g/l, Pentanatriumtriphosphat mit einer Konzentration in einem Bereich von 2 g/l - 20 g/l, und das Anlegen einer Spannung zwischen Lösung und Titanwerkstoff für eine vorgegebene Zeitdauer zur Herstellung der Schicht durch anodische Oxidation der Oberfläche.The object is achieved by a method according to claim 1. The method for producing an adhesion-promoting layer on a surface of a titanium material comprises introducing the surface into an aqueous alkaline solution comprising sodium hydroxide having a concentration in a range of 100-300 g / l, Sodium tartrate having a concentration in a range of 20-200 g / l, methylglycinediacetic acid Na3 having a concentration in a range of 5 g / l - 60 g / l, pentasodium triphosphate having a concentration in a range of 2 g / l - 20 g / l, and applying a voltage between solution and titanium material for a predetermined period of time to produce the layer by anodic oxidation of the surface.

Natriumhydroxid liegt bevorzugt mit einer Konzentration in einem Bereich von 150 - 285 g/l, weiter bevorzugt von 175 - 270 g/l, 195 - 250 g/l, 210 - 240 g/l, 238 - 242 g/l, und speziell von 240 g/l vor.Sodium hydroxide is preferably in the range of 150-285 g / l, more preferably 175-270 g / l, 195-250 g / l, 210-240 g / l, 238-242 g / l, and especially of 240 g / l before.

Natriumtartrat liegt bevorzugt mit einer Konzentration in einem Bereich von 20 - 200 g/l, weiter bevorzugt von 60 - 140 g/l, 75 - 125 g/l, 85 - 110 g/l, 90 - 105 g/l, speziell von 100 g/l vor.Sodium tartrate is preferably at a concentration in a range of 20-200 g / l, more preferably 60-140 g / l, 75-125 g / l, 85-110 g / l, 90-105 g / l, especially of 100 g / l before.

Methylglycindiessigsäure-Na3 liegt bevorzugt mit einer Konzentration in einem Bereich von 10 - 50 g/l, weiter bevorzugt 15 - 40 g/l, 20 - 35 g/l, 25 - 33 g/l, 28 - 32 g/l, speziell von 30 g/l vor.Methylglycinediacetic acid Na3 is preferably present at a concentration in the range of 10-50 g / l, more preferably 15-40 g / l, 20-35 g / l, 25-33 g / l, 28-32 g / l, especially of 30 g / l before.

Pentanatriumtriphosphat liegt bevorzugt mit einer Konzentration von 3 - 17 g/l, weiter bevorzugt von 4,5 - 13 g/l, oder 6 - 10 g/l, oder 7 - 8 g/l, speziell 7,5 g/l vor.Pentasodium triphosphate is preferably present at a concentration of 3-17 g / l, more preferably 4.5-13 g / l, or 6-10 g / l, or 7-8 g / l, especially 7.5 g / l ,

Jeder der vorstehenden Konzentrationsbereiche oder jede Konzentration einer der Bestandteile der Lösung kann mit einem beliebigen Konzentrationsbereich oder einer beliebigen Konzentration eines jeden anderen Bestandteils kombiniert werden.Each of the above concentration ranges or concentrations of one of the constituents of the solution may be combined with any concentration range or concentration of any other constituent.

Es wurde herausgefunden, dass mit Hilfe eines anodischen Oxidierens der Oberfläche des Titanwerkstoffs in der angegebenen alkalischen Lösung eine als Oxidschicht ausgebildete haftvermittelnde Schicht auf der Oberfläche des Titanwerkstoffs geschaffen werden kann, die im Vergleich zum Stand der Technik zumindest gleich gute Haftvermittlungseigenschaften aufweist. Vorteilhaft sind dazu ausschließlich oder zumindest überwiegend umweltfreundliche Inhaltsstoffe notwendig. Natriumhydroxid enthält Na+ Ionen, die von herkömmlichem Kochsalz bekannt sind. Pentanatriumtriphosphat, auch bekannt als Triphosphat ist ein Bestandteil biologischer Verbindungen wie zum Beispiel Adenosintriphosphat. Außerdem ist Pentanatriumtriphosphat als Nahrungsmittelzusatzstoff zugelassen, also im Vergleich zu beim Stand der Technik verwendeten Chemikalien ein besonders harmloser Stoff. Methylglycindiessigsäure-Na3, auch bekannt als Natriumsalz der Methylglycindiessigsäure findet insbesondere als Reinigungsmittel, insbesondere als Geschirrreinigungsmittel Verwendung und ist insofern hinsichtlich Umweltgesichtspunkten unbedenklich. Methylglycindiessigsäure ist auch unter der Bezeichnung MGDA bekannt. Natriumtartrat ist ein Natriumsalz der Weinsäure, ebenfalls als Nahrungsmittelzusatzstoff zugelassen und daher ebenfalls hinsichtlich Umweltgesichtspunkten besonders unbedenklich. Das Natriumtartrat wirkt in der alkalischen Lösung als Titankomplexbildner und kann damit vorteilhaft Rücklöseeigenschaften verbessern. Methylglycindiessigsäure-Na3 wirkt als Fremdionenkomplexbildner und Pentanatriumtriphosphat als Gerüstbildner. Vorteilhaft ist die alkalische Lösung gänzlich fluoridfrei und ermöglicht dennoch eine optimale Vorbehandlung der Oberfläche des Titanwerkstoffs für Langzeitbeständige, hochfeste Anbindungen von organischen Beschichtungen. Unter einem Titanwerkstoff kann reines Titan oder einen Titanlegierung, beispielsweise eine Titanlegierung mit der Bezeichnung Ti6Al4V, verstanden werden.It has been found that by means of an anodic oxidation of the surface of the titanium material in the specified alkaline solution, an adhesion-promoting layer in the form of an oxide layer can be provided on the surface of the titanium material, which has at least as good adhesion-promoting properties as in the prior art. Advantageously, exclusively or at least predominantly environmentally friendly ingredients are necessary. Sodium hydroxide contains Na + ions, which are known from conventional saline. Pentasodium triphosphate, also known as triphosphate, is a component of biological compounds such as adenosine triphosphate. In addition, pentasodium triphosphate is approved as a food additive, so compared to chemicals used in the prior art is a particularly harmless substance. Methylglycinediacetic acid Na 3 , also known as the sodium salt of methylglycinediacetic acid, is used in particular as a cleaning agent, in particular as a dishwashing detergent, and is insofar harmless from an environmental point of view. Methylglycinediacetic acid is also known as MGDA. Sodium tartrate is a sodium salt of tartaric acid, also approved as a food additive and therefore also particularly harmless from an environmental point of view. The sodium tartrate acts as a titanium complexing agent in the alkaline solution and can thus advantageously improve the return properties. Methylglycinediacetic acid Na 3 acts as a foreign ion complexing agent and pentasodium triphosphate as a scaffolding agent. Advantageously, the alkaline solution is completely fluoride-free and yet allows optimum pretreatment of the surface of the titanium material for long-term stable, high-strength bonds of organic coatings. A titanium material may be understood to be pure titanium or a titanium alloy, for example a titanium alloy with the designation Ti6Al4V.

Bei einer weiteren Ausführungsform des Verfahrens wird die anodische Oxidation vorteilhaft mit einer Spannung in einem Bereich von 2 - 50 V, bevorzugt 3 - 45 V, 5 - 35 V, 7 - 25 V, 9 - 20 V, 9 - 15 V, 10 - 12 V, speziell von 10 V vorgenommen. Bei der angegebenen Spannung kann die vorteilhafte Oxidschicht erzeugt werden.In a further embodiment of the method, the anodization is advantageously carried out with a voltage in a range of 2 to 50 V, preferably 3 to 45 V, 5 to 35 V, 7 to 25 V, 9 to 20 V, 9 to 15 V, 10 - 12 V, specially made by 10 V. At the specified voltage, the advantageous oxide layer can be produced.

Bei einer weiteren Ausführungsform des Verfahrens wird die anodische Oxidation der Oberfläche vorteilhaft für eine Zeitdauer vorgenommen, in der die vorteilhafte haftvermittelnde Schicht auf der Oberfläche des Titanwerkstoffs erzeugt werden kann. Die Zeitdauer liegt dabei in einem Bereich von 5 - 60 min, bevorzugt 8 - 50 min, 11 - 40 min, 15 - 30 min, 18 - 25 min, 19 - 22 min, speziell 20 min.In a further embodiment of the method, the anodic oxidation of the surface is advantageously carried out for a period of time in which the advantageous adhesion-promoting layer can be produced on the surface of the titanium material. The period of time is in a range of 5 to 60 minutes, preferably 8 to 50 minutes, 11 to 40 minutes, 15 to 30 minutes, 18 to 25 minutes, 19 to 22 minutes, especially 20 minutes.

Bei einer weiteren Ausführungsform des Verfahrens ist die anodische Oxidation vorteilhaft bei einer maximale Stromdichte vorgesehen, bei der die vorteilhafte haftvermittelnde Schicht auf der Oberfläche des Titanwerkstoffs erzeugt werden kann. Die maximale Stromdichte liegt in einem Bereich von 0,2 - 10 A/dm2, bevorzugt 0,4 - 8 A/dm2, 0,6 - 4 A/dm2, 0,8 - 2 A/dm2, 1,0 - 1,5 A/dm2, 1,1 - 1,3 A/dm2, speziell von 1,2 A/dm2.In a further embodiment of the method, the anodic oxidation is advantageously provided at a maximum current density at which the advantageous adhesion-promoting layer can be produced on the surface of the titanium material. The maximum current density is in a range of 0.2 - 10 A / dm 2 , preferably 0.4 - 8 A / dm 2 , 0.6 - 4 A / dm 2 , 0.8 - 2 A / dm 2 , 1 , 0-1.5 A / dm 2 , 1.1-1.3 A / dm 2 , especially of 1.2 A / dm 2 .

Bei einer weiteren Ausführungsform des Verfahrens ist die anodische Oxidation vorteilhafte bei einer Temperatur vorgesehen, bei der die vorteilhafte haftvermittelnde Schicht auf der Oberfläche des Titanwerkstoffs erzeugt werden kann. Die Temperatur liegt in einem Bereich von betragen 5 - 60 °C, bevorzugt 10 - 50 °C, 15 - 40 °C, 20 - 35 °C, 25 - 33 °C, 28 - 32 °C, speziell 30 °C.In a further embodiment of the method, the anodization is advantageous at a temperature at which the advantageous adhesion-promoting layer can be produced on the surface of the titanium material. The temperature is in a range of 5 to 60 ° C, preferably 10 to 50 ° C, 15 to 40 ° C, 20 to 35 ° C, 25 to 33 ° C, 28 to 32 ° C, especially 30 ° C.

Jeder Bereich oder Wert eines der vorstehenden Merkmale kann mit einem beliebigen Bereich oder Wert eines jeden anderen Merkmals oder einer beliebigen Kombination von Konzentrationsbereichen oder Konzentrationen der gelösten Bestandteile kombiniert werden.Any range or value of any of the above features may be combined with any range or value of any other feature or combination of concentration ranges or concentrations of the solutes.

Bei einer weiteren Ausführungsform des Verfahrens ist eine anodische Oxidation der Oberfläche der alkalischen Lösung und dadurch das Erzeugen einer Oxidschicht der Schichtdicke in einem Bereich von 50 - 600 nm, bevorzugt 70 - 400 nm, 100 - 250 nm, , speziell von 150 nm vorgesehen. Vorteilhaft kann bei der angegebenen Schichtdicke eine besonders gute Haftvermittlung erzeugt werden.In a further embodiment of the method, anodic oxidation of the surface of the alkaline solution and thereby the production of an oxide layer of the layer thickness in a range of 50-600 nm, preferably 70-400 nm, 100-250 nm, especially of 150 nm is provided. Advantageously, a particularly good adhesion promotion can be generated at the specified layer thickness.

Die Aufgabe wird außerdem durch eine haftvermittelnde Schicht auf einer Oberfläche eines Titanwerkstoffs, herstellbar oder hergestellt nach einem vorab beschriebenen Verfahren gelöst, gemäß Anspruch 11. Die Oberfläche des Titanwerkstoffs weist insbesondere eine poröse Nanostruktur mit nebeneinander angeordneten Erhebungen mit Hinterschnitten sowie insbesondere eine Interferenzfärbung auf. Die einzelnen Strukturen sind in der Größenordnung von 50-300 nm. Vorteilhaft kann die haftvermittelnde Schicht auf der Oberfläche des Titanwerkstoffs langzeitstabil und mit besonders guten Hafteigenschaften mit organischem Material beschichtet und/oder versehen werden. Außerdem kann mittels der Interferenzfärbung erkannt werden, dass die gewünschte haftvermittelnde Schicht auf der Oberfläche des Titanwerkstoffs auch tatsächlich vorhanden ist bzw. dass der Titanwerkstoff auf seiner Oberfläche die haftvermittelnde Schicht aufweist. Im Übrigen ergeben sich die vorab beschriebenen Vorteile.The object is also achieved by an adhesion-promoting layer on a surface of a titanium material, produced or prepared according to a previously described Method solved according to claim 11. The surface of the titanium material has in particular a porous nanostructure with juxtaposed elevations with undercuts and in particular an interference coloring on. The individual structures are on the order of 50-300 nm. Advantageously, the adhesion-promoting layer on the surface of the titanium material can be coated and / or provided with organic material with long-term stability and with particularly good adhesive properties. In addition, it can be recognized by means of interference coloring that the desired adhesion-promoting layer is actually present on the surface of the titanium material or that the titanium material has the adhesion-promoting layer on its surface. Incidentally, the advantages described above arise.

Weitere Vorteile, Merkmale und Einzelheiten ergeben sich aus der nachfolgenden Beschreibung, in der - gegebenenfalls unter Bezug auf die Zeichnung - zumindest ein Ausführungsbeispiel im Einzelnen beschrieben ist. Beschriebene und/oder bildlich dargestellte Merkmale bilden für sich oder in beliebiger, sinnvoller Kombination den Gegenstand der Erfindung, gegebenenfalls auch unabhängig von den Ansprüchen, und können insbesondere zusätzlich auch Gegenstand einer oder mehrerer separaten Anmeldung/en sein. Gleiche, ähnliche und/oder funktionsgleiche Teile sind mit gleichen Bezugszeichen versehen.Further advantages, features and details will become apparent from the following description in which - where appropriate, with reference to the drawings - at least one embodiment is described in detail. Described and / or illustrated features form the subject of the invention, or independently of the claims, either alone or in any meaningful combination, and in particular may additionally be the subject of one or more separate applications. The same, similar and / or functionally identical parts are provided with the same reference numerals.

Es zeigen:

Fig. 1
eine schematische Ansicht einer Vorrichtung zum Durchführen eines Verfahrens zum anodischen Oxidieren einer Oberfläche eines Titanwerkstoffs in einer alkalischen Lösung;
Fig. 2
eine Draufsicht auf eine mittels anodischen Oxidierens nanostrukturierte Oxidschicht auf der Oberfläche eines Titanwerkstoffs; und
Figur 3
einen Kryobruch der in Figur 2 gezeigten Oberfläche auf dem Titanwerkstoff.
Show it:
Fig. 1
a schematic view of an apparatus for performing a method for anodizing a surface of a titanium material in an alkaline solution;
Fig. 2
a plan view of an anodized oxide nanostructured oxide layer on the surface of a titanium material; and
FIG. 3
a cryobreak of in FIG. 2 surface shown on the titanium material.

Figur 1 zeigt eine schematische Ansicht einer Vorrichtung 1 zur Herstellung einer haftvermittelnden Schicht auf einer Oberfläche 3 eines Titanwerkstoffs 5. Die Vorrichtung 1 weist ein Bad 7 mit einem Elektrolyt 9 auf. Der Elektrolyt 9 weist Natriumhydroxid, Natriumtartrat, Methylglycindiessigsäure-Na3 sowie Pentanatriumtriphosphat in einer wässrigen Lösung auf. Zum Erzeugen einer in Figur 1 nicht näher dargestellten Oxidschicht sind der Titanwerkstoff 5 und das Bad 7 an eine elektrische Energiequelle 11 angeschlossen, wobei über den Elektrolyt 9 des Bades 7 ein Stromkreis geschlossen wird. Die elektrische Energiequelle 11 liefert eine Spannung 13, die einen Strom 15 in dem über den Elektrolyt 9 geschlossenen Stromkreis bewirkt. Gegebenenfalls können nicht näher dargestellte Steuer- und/oder Regelvorrichtungen zum Einstellen der Spannung 13 und/oder des Stromes 15 vorgesehen sein. FIG. 1 1 shows a schematic view of a device 1 for producing an adhesion-promoting layer on a surface 3 of a titanium material 5. The device 1 has a bath 7 with an electrolyte 9. The electrolyte 9 comprises sodium hydroxide, sodium tartrate, methylglycinediacetic acid-Na 3 and pentasodium triphosphate in an aqueous solution. To create an in FIG. 1 not shown oxide layer of the titanium material 5 and the bath 7 are connected to an electrical energy source 11, wherein via the electrolyte 9 of the bath 7, a circuit is closed. The electrical energy source 11 supplies a voltage 13, which causes a current 15 in the closed circuit via the electrolyte 9. Optionally, not shown in detail control and / or regulating devices for adjusting the voltage 13 and / or the current 15 may be provided.

Mittels der Vorrichtung 1 kann durch anodisches Oxidieren eine in den Figuren 2 und 3 dargestellte Oxidschicht 17 auf der Oberfläche 3 des Titanwerkstoffs 5 erzeugt werden. Maßstäbe sind in den Figuren 2 und 3 jeweils mit einer Linie, die mit einer Längenangabe in nm beschriftet sind, eingezeichnet.By means of the device 1 can by anodizing an in the Figures 2 and 3 shown oxide layer 17 are generated on the surface 3 of the titanium material 5. Standards are in the Figures 2 and 3 each with a line, which are labeled with a length in nm, drawn.

Mittels des anodischen Oxidierens wird die haftvermittelnde Schicht auf der Oberfläche 3 des Titanwerkstoffs 5 hergestellt. Dazu wird zunächst die Oberfläche 3 in das die alkalische Lösung bzw. den Elektrolyt 9 enthaltende Bad 7 eingebracht, beispielsweise durch zumindest teilweises Eintauchens des Titanwerkstoffs 5 in den Elektrolyt 9. Im eingebrachten Zustand der Oberfläche 3 wird die Spannung 13 zwischen dem Elektrolyt 9 und dem Titanwerkstoff 5 für eine vorgegebene Zeitdauer zur Herstellung der Schicht durch anodische Oxidation der Oberfläche 3 des Titanwerkstoffs 5 hergestellt.By means of anodizing, the adhesion-promoting layer is produced on the surface 3 of the titanium material 5. For this purpose, the surface 3 is first introduced into the alkaline solution or the electrolyte 9 containing bath 7, for example, by at least partial immersion of the titanium material 5 in the electrolyte 9. In the introduced state of the surface 3, the voltage 13 between the electrolyte 9 and the Titanium material 5 for a predetermined period of time for the preparation of the layer by anodic oxidation of the surface 3 of the titanium material 5 produced.

Figur 2 zeigt eine Draufsucht auf die Oberfläche 3 des Titanwerkstoffs 5. FIG. 2 shows a thirst for the surface 3 of the titanium material. 5

Figur 3 zeigt einen Kryobruch des Titanwerkstoffs 5 zusammen mit der Oberfläche 3, wobei die Oxidschicht 17 zu erkennen ist. Mittels eines Doppelpfeiles 19 ist in Figur 3 eine Dicke der Oxidschicht 17 symbolisiert, wobei diese ungefähr 150 nm beträgt. FIG. 3 shows a cryogenic fracture of the titanium material 5 together with the surface 3, wherein the oxide layer 17 can be seen. By means of a double arrow 19 is in FIG. 3 a thickness of the oxide layer 17 symbolizes, which is about 150 nm.

In den Figuren 2 und 3 ist zu erkennen, dass die Oxidschicht 17 eine ausgeprägte Mikroporöse Nanostruktur aufweist, wobei diese knollenartige Auswüchse, die nebeneinander angeordnet sind, aufweist. Die knollenartigen Auswüchse weisen eine Dimension von kleiner als 300 nm, insbesondere kleiner als 250 nm, insbesondere kleiner als 200 nm, insbesondere kleiner als 150 nm, vorzugsweise kleiner als 50 nm bis 100 nm auf und bilden eine vorteilhafte mikroporöse Oberfläche.In the Figures 2 and 3 It can be seen that the oxide layer 17 has a pronounced microporous nanostructure, with these bulbous outgrowths arranged side by side. The bulbous outgrowths have a dimension of less than 300 nm, in particular less than 250 nm, in particular less than 200 nm, in particular less than 150 nm, preferably less than 50 nm to 100 nm, and form an advantageous microporous surface.

Bevorzugtes AusführungsbeispielPreferred embodiment

Zum Herstellen der in den Figuren 2 und 3 dargestellten Oxidschicht 17 auf der Oberfläche 3 des Titanwerkstoffs 5 wird das Bad 7 mit dem Elektrolyt 9 der Zusammensetzung 240 g/l Natriumhydroxid, 100 g/l Natriumtartrat, 30 g/l Methylglycindiessigsäure-Na3, und 7,5 g/l Pentanatriumtriphosphat gefüllt.For making the in the Figures 2 and 3 illustrated oxide layer 17 on the surface 3 of the titanium material 5, the bath 7 with the electrolyte 9 of the composition 240 g / l sodium hydroxide, 100 g / l sodium tartrate, 30 g / l methylglycinediacetic-Na 3 , and 7.5 g / l pentasodium triphosphate filled ,

Die Oberfläche 3 des Titanwerkstoffs 5 wird zumindest teilweise in das Bad 7 eingebracht, insbesondere eingetaucht.The surface 3 of the titanium material 5 is at least partially introduced into the bath 7, in particular immersed.

An den zumindest teilweise eingetauchten Titanwerkstoff 5 und das Bad 7 wird mittels der elektrischen Energiequelle 11 die Spannung 13 mit 10 V angelegt. Der Strom 15 wird so eingestellt, dass auf der Oberfläche 3 des Titanwerkstoffs 5 eine Stromdichte von maximal von 1,2 A/dm2 auftritt. Die Spannung 13 und der Strom 15 und damit die Stromdichte von 1,2 A/dm2 werden für eine Zeitdauer von 20 Minuten aufrechterhalten. Das Bad 7 wird auf eine Temperatur von 30 °C temperiert. Gegebenenfalls können zum Einstellen der Temperatur von 30 °C nicht näher dargestellte Temperatureinstellvorrichtungen, beispielsweise eine Heizung und/oder eine Kühlung vorgesehen sein.To the at least partially immersed titanium material 5 and the bath 7, the voltage 13 is applied by 10 V by means of the electric power source 11. The current 15 is adjusted so that a current density of at most 1.2 A / dm 2 occurs on the surface 3 of the titanium material 5. The voltage 13 and the current 15 and thus the current density of 1.2 A / dm 2 are maintained for a period of 20 minutes. The bath 7 is heated to a temperature of 30 ° C. Optionally, to set the temperature of 30 ° C not closer represented Temperaturinstellvorrichtungen, for example, a heater and / or cooling can be provided.

Zusammenfassend kann die gewünschte nanostrukturierte Oberfläche 3, also die Oxidschicht 17 in einem gänzlich fluoridfreien Verfahren zur Vorbehandlung des Titanwerkstoffes 5 zum Erzielen von langzeitbeständigen, hochfesten Anbindungen von organischen Beschichtungen erzielt werden.In summary, the desired nanostructured surface 3, ie the oxide layer 17, can be achieved in a completely fluoride-free process for the pretreatment of the titanium material 5 in order to achieve long-term stable, high-strength bonds of organic coatings.

Vorteilhaft kann dies durch die mikro-/nanostrukturierte Oxidschicht 17 erzielt werden. Vorteilhaft kann die beschriebene poröse Oberflächenmorphologie auf dem Titanwerkstoff 5 erzeugt werden. Diese kann haftfest beschichtet werden, beispielsweise mit organischen Materialien wie Klebstoff, Lack, Dichtstoff und/oder Ähnlichem.This can advantageously be achieved by the microstructured / nanostructured oxide layer 17. Advantageously, the described porous surface morphology can be produced on the titanium material 5. This can be adherent coated, for example with organic materials such as adhesive, paint, sealant and / or the like.

Vorteilhaft ist der Elektrolyt 9 nicht nur fluoridfrei, sondern enthält ausschließlich oder zumindest überwiegend umweltfreundliche Inhaltsstoffe, die insbesondere biologisch abbaubar sind.Advantageously, the electrolyte 9 is not only fluoride-free, but contains exclusively or at least predominantly environmentally friendly ingredients that are particularly biodegradable.

Die Interferenzfärbung kann als Nachweis für die durchgeführte Behandlung und/oder als Identifikationsmerkmal für entsprechende behandelte Bauteile aus dem Titanwerkstoff 5 dienen.The interference coloring can serve as proof of the treatment carried out and / or as an identification feature for corresponding treated components made of the titanium material 5.

Alternativ und/oder zusätzlich kann die Oxidschicht 17 auf der Oberfläche 3 des Titanwerkstoffs 5 auch zur Anbindung von biologischem Material verwendet werden, beispielsweise auf Implantaten.Alternatively and / or additionally, the oxide layer 17 on the surface 3 of the titanium material 5 can also be used for bonding biological material, for example on implants.

Alternativ und/oder zusätzlich ist es denkbar, dass die Lösung zumindest in Spuren und/oder als zumindest teilweiser Ersatz vorhandener Ionen weitere Bestandteile aufweist, insbesondere Ionen derselben Periode eines Periodensystems.Alternatively and / or additionally, it is conceivable that the solution has at least in traces and / or as at least partial replacement of existing ions further constituents, in particular ions of the same period of a periodic table.

BezugszeichenlisteLIST OF REFERENCE NUMBERS

11
Vorrichtungcontraption
33
Oberflächesurface
55
TitanwerkstoffTitanium material
77
Badbath
99
Elektrolytelectrolyte
1111
elektrische Energiequelleelectrical energy source
1313
Spannungtension
1515
Stromelectricity
1717
Oxidschichtoxide
1919
Doppelpfeildouble arrow

Claims (11)

  1. Method for producing an adhesion-promoting layer on the surface (3) of a titanium workpiece (5), comprising:
    - introducing the surface (3) into an aqueous alkaline solution comprising sodium hydroxide at a concentration in a range of 100 - 300 g/l, sodium tartrate at a concentration in a range of 20 g/l - 200 g/l, methylglycinediacetic acid-Na3 at a concentration in a range of 5 g/l - 60 g/l, pentasodium triphosphate at a concentration in a range of 2 g/l - 20 g/l, and
    - applying a voltage (13) between the solution and the titanium workpiece (5) for a predetermined period of time so as to produce the layer by means of anodic oxidation of the surface (3).
  2. Method according to Claim 1, in which sodium hydroxide is present at a concentration in a range of 150 - 285 g/l, further preferably of 175 - 270 g/l, 195 - 250 g/l, 210 - 240 g/l, 238-242 g/l, specifically 240 g/l.
  3. Method according to Claim 1 or 2, in which sodium tartrate is present at a concentration in a range of 20 - 200 g/l, further preferably from 60 - 140 g/l, 75 - 125 g/l, 85 - 110 g/l, 90 - 105 g/l, specifically of 100 g/l.
  4. Method according to any one of the claims 1 to 3 in which methylglycinediacetic acid-Na3 is present at a concentration in a range of 10 - 50 g/l, further preferably 15 - 40 g/l, 20 - 35 g/l, 25 - 33 g/l, 28 - 32 g/l, specifically of 30 g/l.
  5. Method according to any one of the claims 1 to 4, in which sodium triphosphate is present at a concentration of 3 - 17 g/l, further preferably 4.5 - 13 g/l, or 6 - 10 g/l, or 7 - 8 g/l, specifically 7.5 g/l.
  6. Method according to any one of the preceding claims, in which the anodic oxidation is performed with a voltage (13) in a range of 2 - 50 V, preferably 3 - 45 V, 5 - 35 V, 7 - 25 V, 9 - 20 V, 9 - 15 V, 10 - 12 V, specifically 10 V.
  7. Method according to any one of the preceding claims in which the anodic oxidation is performed for a period of time in a range of 5 - 60 min, preferably 8 - 50 min, 11 - 40 min, 15 - 30 min, 18 - 25 min, 19 - 22 min, specifically 20 min.
  8. Method according to any one of the preceding claims, in which the anodic oxidation in the case of a maximum current density is performed in a range of 0.2 - 10 A/dm2, preferably 0.4 - 8 A/dm2, 0.6 - 4 A/dm2, 0.8 - 2 A/dm2, 1.0 - 1.5 A/dm2, 1.1 - 1.3 A/dm2, specifically of 1.2 A/dm2.
  9. Method according to any one of the preceding claims in which the anodic oxidation is performed at a temperature in a range of 5 - 60 °C, preferably 10 - 50 °C, 15 - 40 °C, 20 - 35 °C, 25 - 33 °C, 28 - 32 °C, specifically 30 °C.
  10. Method according to any one of the preceding claims in which the anodic oxidation of the surface is performed in the alkaline solution when generating an oxide layer having a layer thickness in a range of 50 - 600 nm, preferably 70 - 400 nm, 100 - 250 nm, specifically of 150 nm.
  11. Adhesion-promoting layer on a surface (3) of a titanium workpiece (5) that can be produced or is produced according to a method according to any one of the previous claims, wherein the adhesion-promoting layer comprises a porous nanostructure having adjacent raised areas with undercuts and also an interference colouring.
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US3400058A (en) * 1965-09-21 1968-09-03 Boeing Co Electrochemical process for andic coating of metal surfaces
US3907609A (en) 1974-02-14 1975-09-23 Mc Donnell Douglas Corp Conversion coating for titanium and titanium base alloys
US4394224A (en) 1980-04-24 1983-07-19 British Aerospace Public Limited Company Treatment of titanium prior to bonding
US4473446A (en) 1981-05-01 1984-09-25 The Boeing Company Chromic acid-fluoride anodizing surface treatment for titanium
DE3206470A1 (en) * 1982-02-23 1983-09-01 Hoechst Ag, 6230 Frankfurt METHOD FOR THE PRODUCTION OF CARRIER MATERIALS FOR OFFSET PRINTING PLATES
FR2556011B1 (en) * 1983-12-01 1992-08-07 Messerschmitt Boelkow Blohm PROCESS FOR THE SURFACE TREATMENT OF TITANIUM PARTS
DE3427543A1 (en) 1983-12-01 1985-07-04 Messerschmitt-Bölkow-Blohm GmbH, 2800 Bremen METHOD FOR TREATMENT OF WORKPIECES FROM TITANIUM
DE3802043C1 (en) 1988-01-25 1989-07-06 Espe Stiftung & Co Produktions- Und Vertriebs Kg, 8031 Seefeld, De Process for preparing a metal surface for bonding to plastic by applying a silicon-containing layer, and use of silicon-containing material
JP3274232B2 (en) * 1993-06-01 2002-04-15 ディップソール株式会社 Tin-bismuth alloy plating bath and plating method using the same
US6037060A (en) 1996-11-04 2000-03-14 The Boeing Company Sol for bonding expoxies to aluminum or titanium alloys
US5814137A (en) 1996-11-04 1998-09-29 The Boeing Company Sol for coating metals
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