DD156003A1 - Process for surface treatment of titanium and alloys - Google Patents

Process for surface treatment of titanium and alloys Download PDF

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Publication number
DD156003A1
DD156003A1 DD22405580A DD22405580A DD156003A1 DD 156003 A1 DD156003 A1 DD 156003A1 DD 22405580 A DD22405580 A DD 22405580A DD 22405580 A DD22405580 A DD 22405580A DD 156003 A1 DD156003 A1 DD 156003A1
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DD
German Democratic Republic
Prior art keywords
titanium
tit tit
metallic
particular
characterized
Prior art date
Application number
DD22405580A
Other languages
German (de)
Inventor
Peter Kurze
Guenter Marx
Waldemar Krysmann
Karl-Heinz Dittrich
Original Assignee
Peter Kurze
Guenter Marx
Waldemar Krysmann
Dittrich Karl Heinz
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Peter Kurze, Guenter Marx, Waldemar Krysmann, Dittrich Karl Heinz filed Critical Peter Kurze
Priority to DD22405580A priority Critical patent/DD156003A1/en
Publication of DD156003A1 publication Critical patent/DD156003A1/en

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Abstract

In a one-step process, a spark discharge in an aqueous electrolyte at the electrolyte / titanium phase boundary is carried out using DC and / or alternating and pulsed voltages such that titanium ions as defined by varying the reaction time in structure and properties as well as oxide layers with disperse intercalations and metallic deposits are generated. The electrolytes are acidic as well as basic and in particular contain the anions fluoride and / or phosphates and / or carbonate and / or sulfate and / or borate and / or citrate and / or borofluorate, preferably close to the saturation concentration. The electrolyte may further ionogenic additives such as the anions silicate, aluminate, zincate, molybdate, chromate, vanadate and cations of the metals Pt, Pd, Ni, Cr and metallic and non-metallic components are added. The spark discharge is carried out at current densities, 100 A / dm high 2 and at working voltages 10-20 V higher than the ignition voltage. The titanium oxidized by the process according to the invention can be used in the chemical industry, aerospace and medical technology.

Description

Move η to the surface of ribeh.analu.ng of titanium and alloys

Field of application of the invention

The invention includes a process for the surface treatment of titanium and alloys using oxidation under spark discharge in aqueous electrolytes. «

The oxide coatings on titanium or alloys produced in this way have good corrosion protection, thermal conductivity and electrical properties 0

The titanium oxidized by the process according to the invention can be used as non-dissolvable passive electrode z. B. in the chemical industry as well as in electrochemical metalworking, in space technology z. B. as a heat shield and in medical technology as an implant.

Characteristic of the known technical solutions

It is known to oxidize titanium or alloys, which can be oxidized by plasma oxidation in an oxygen atmosphere. Air atmosphere occur, as described in the patent applications DIi-OS 2552 972 and CH 470 490. "The disadvantage of this method is that high energy and a lot of equipment and time are required." In addition, only oxides in the stoichiometric composition .TiO ,,,. with.χ = 0.35 * Further can be obtained by chemical oxidation, especially in aqueous

and / or nonaqueous media. Titanium passivated. The resulting layers are few / strong and have insufficient passive behavior for the intended applications. Therefore, it is attempted to replace this chemical oxidation process by an electrochemical. In this case колипеп aqueous and / or non-aqueous electrolytes used, as it is z. B. in the invention applications US 3928 112, SU 197 540 and DD 89 769 is set out * It is achieved thicker oxide layer thicknesses · The oxides have partially defined structures. The disadvantage of these methods is that they are very time-consuming and often only in the two-stage process by "feasible. In addition, disadvantageous salt melts or extremely reactive compounds such as, "B, HClO ^, or their salts are used

Object of the invention

The aim of the invention is to eliminate the stated disadvantages and to produce selectively stoichiometric as well as doped with impurities titanium oxide layers «

Explanation of the invention of the invention

The invention has for its object to provide a process for the production of corrosion-resistant and adherent., Good thermal conductivity, hard, wear-resistant and electrically semiconducting Titaniiunoxidschichten on titanium and its alloys using aqueous electrolytes and application of .Funkenentladung to develop »

According to the invention the object is achieved in that using aqueous basic and acidic electrolytes in particular consisting of the anions fluoride and / or phosphate and / or sulfate and / or carbonate and / or citrate and / - or borate and / or. Borof luorat in the concentrations near the saturation concentration, in particular 0.5 to 1j5 mol / 1 at temperatures of the electrolyte of 20 90 0 C and using pure DC and / or alternating and

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the avalanche-like "rastering" values> 100 A / dm give * The exchanged energy is determined by the formation of the partial anode and the working voltage. At a higher working voltage than the ignition voltage, thicker and harder layers are produced «The ignition voltage depends on the electrolytic composition and other parameters of the electrolyte such as viscosity, pH, temperature, specific conductivity.« The ignition voltage of the electrolytes used in particular is> 100 V < 220 V. It is advantageous to carry out the oxidation at working voltages which are 10-20 V higher than the starting voltages, since an arbitrary increase in the working voltage, in addition to a high material removal, leads to uncontrollable layer compositions. It is expedient to continuously increase the potential from the active via the transpassive region to the ignition. Thereafter, the working voltage is increased discretely by a fixed value of 10-20 V. "The choice of the treatment time significantly influences the stoichiometry of the oxide formed." After the avalanche-like scanning which takes place with a high degree of

If the discharge rate is <20 As / cm, an oxide with an oxygen content <1 will be generated. Oxygen content formed up to TiOp. The oxidation process is characterized by the different color of the oxides. The oxide layers are formed by the addition of foreign ions in the electrolyte such. B 0 chromate, vanadate, silicate, tungstate, zincate, aluminate doped. The foreign ions can also be present as cations, in particular of Pt, Pd, Ni, Cr, etc., and are deposited in and on the layer during a cathodic reaction phase. As a result, a variety of mixed oxides can be produced, which also have pronounced catalytic properties.

From aqueous suspensions z. B, carbides such as tungsten, titanium, chromium carbide and / or oxides such as SiO- »TiO-» ZnO, MgO, CiO-Al 2 Oo u. a, and / or metallic such as Pt, Pd, Ag, etc. »and / or non-metallic components such as B u, a. contain dispersion layers are deposited, which in turn allow a wide modification of the properties, such as increasing the corrosion and wear resistance, improving the catalytic effect u. a ». The generation of the modified titanium oxide layers is positively influenced by short-term voltage interruptions and superimposition of pulse voltages with dead times> 0.5 s.

embodiment

The invention will be described below with reference to three exemplary embodiments »

Embodiment 1

In an aqueous solution which is 0.5% of phosphate, 0.5% of carbonate and 0.5% of fluoride, under the influence of a pure DC voltage of 150 V and an electrolyte temperature of 60 ° C., a titanium sheet is obtained Methods are pickled bare metal, anodically coated with spark discharge at a constant current of 4 A,

after a reaction time of 1 min, the coating is interrupted and oin oxide of gray-blue color is obtained. The layer thickness is determined to be 10 / μm. The microhardness of

о layer is more than 460 kgf / mm "," v / o in the hardness of the Gründme-

ρ tails to 360 kp / mm is determined »

Embodiment 2

In an electrolyte, which is 0.8 m of eluoride and 0.8 m of phosphate, is under the action of a pulse current superimposed DC voltage spark oxidation on a previously pickled, anodically poled titanium sheet at an electrolyte temperature of 30 C 3 min. long performed. The pure DC voltage is 1/3 of the pulse voltage, which is set to 150V. The pulse frequency is 0.2 pulses / s with a pulse length of 2s.

Layer thicknesses> 15 / μm and microhardness of the layer> 500 kp / mm 2 are obtained.

Embodiment 3

In the electrolyte according to Embodiment 1, 0.05 m. Sodium silicate and 15 g / l boron, tungsten and titanium carbide added and homogenized. The DC voltage is continuously increased up to the ignition voltage at a feed rate of 85 V / min. The scanning is carried out in 5 cycles per 15 s. The sintered layers have layer thicknesses> 20 лип, are very hard and partially porous.

Claims (5)

Erfimdumgsaiuspruch
1. A process for the surface treatment of titanium and alloys in aqueous electrolytes, characterized in that using DC and / or alternating and pulse voltages, a spark discharge is carried out so that in a one-step process by the variation of the reaction time in structure and properties defined titanium oxides as well as oxide layers with disperse inclusions and / or metallic deposits are generated ·
Method according to item 1, characterized in that the aqueous electrolyte solutions are acidic as well as basic and in particular the anions comprise fluoride and / or phosphate and / or sulfate and / or borate and / or citrate and / or borofluorate preferably close to the saturation concentration,
3 «method according to item 1 and 2, characterized in that in the electrolyte ionogenic additives of anions in particular silicate, aluminate, zincate, molybdate, chromate, vanadate and cations in particular the metals Pt, Pd, Ni, Cr and / or disperse components in particular Carbides such as tungsten, titanium, chromium carbide and / or oxides such as SiO 2 »TiO 2 * ZnO, MgO, Oo-AlJD ^ and metallic and non-metallic components in particular B are also included
4 · Method according to items 1 to 3, characterized in that
the spark discharge is carried out at current densities> 100 A / dm and at working voltages 10-20 V higher than the ignition voltage ·
5. The method according to item 1 to Ц- characterized in that the oxidation of the titanium and the formation of the dispersion is effected by DC superimposed with pulse current, which is both continuously increased up to a ratio of 3 s 1 or "discretely specified especially at pulse frequencies of 0.2 pulses / s and pulse lengths of 2 s.
DD22405580A 1980-09-23 1980-09-23 Process for surface treatment of titanium and alloys DD156003A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DD22405580A DD156003A1 (en) 1980-09-23 1980-09-23 Process for surface treatment of titanium and alloys

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DD22405580A DD156003A1 (en) 1980-09-23 1980-09-23 Process for surface treatment of titanium and alloys

Publications (1)

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DD156003A1 true DD156003A1 (en) 1982-07-21

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2651509A1 (en) * 1989-09-04 1991-03-08 Dipsol Chem Process for the production of ceramic films by spark discharge from anode.
DE19910188C2 (en) * 1998-11-02 2001-05-10 Wolfgang Brandau Implant, process for its preparation and its use
DE4139006C3 (en) * 1991-11-27 2003-07-10 Electro Chem Eng Gmbh A process for producing oxide ceramic layers on barrier layer-forming metals and in this way generated objects made of aluminum, magnesium, titanium or alloys thereof with an oxide ceramic layer
DE102009016554A1 (en) 2009-02-19 2010-09-09 Heraeus Kulzer Gmbh Medical implant i.e. dental implant, for implanting in human body, has metallic body comprising surface layer which contains calcium and/or phosphorus, where zirconium and/or zirconium dioxide are stored in surface layer
DE102011007424A1 (en) * 2011-04-14 2012-10-18 Helmholtz-Zentrum Geesthacht Zentrum für Material- und Küstenforschung GmbH A process for producing a coating on the surface of a substrate based on light metals by plasma electrolytic oxidation

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2651509A1 (en) * 1989-09-04 1991-03-08 Dipsol Chem Process for the production of ceramic films by spark discharge from anode.
DE4027999A1 (en) * 1989-09-04 1991-03-14 Dipsol Chem Forming ceramic film or layer on surface of substrate - by spark discharge in electrolytic bath contg. aq. soln. of water soluble silicate dispersed in fine ceramic particles
GB2237030A (en) * 1989-09-04 1991-04-24 Dipsol Chem Forming ceramics films by anode-spark discharge in electrolytic bath
US5147515A (en) * 1989-09-04 1992-09-15 Dipsol Chemicals Co., Ltd. Method for forming ceramic films by anode-spark discharge
GB2237030B (en) * 1989-09-04 1994-01-12 Dipsol Chem Method for forming ceramics films by anode-spark discharge
DE4139006C3 (en) * 1991-11-27 2003-07-10 Electro Chem Eng Gmbh A process for producing oxide ceramic layers on barrier layer-forming metals and in this way generated objects made of aluminum, magnesium, titanium or alloys thereof with an oxide ceramic layer
DE19910188C2 (en) * 1998-11-02 2001-05-10 Wolfgang Brandau Implant, process for its preparation and its use
US6709379B1 (en) 1998-11-02 2004-03-23 Alcove Surfaces Gmbh Implant with cavities containing therapeutic agents
DE102009016554A1 (en) 2009-02-19 2010-09-09 Heraeus Kulzer Gmbh Medical implant i.e. dental implant, for implanting in human body, has metallic body comprising surface layer which contains calcium and/or phosphorus, where zirconium and/or zirconium dioxide are stored in surface layer
DE102011007424A1 (en) * 2011-04-14 2012-10-18 Helmholtz-Zentrum Geesthacht Zentrum für Material- und Küstenforschung GmbH A process for producing a coating on the surface of a substrate based on light metals by plasma electrolytic oxidation
DE102011007424B4 (en) * 2011-04-14 2014-01-23 Helmholtz-Zentrum Geesthacht Zentrum für Material- und Küstenforschung GmbH A process for producing a coating on the surface of a substrate based on light metals by plasma electrolytic oxidation and coated substrate
DE102011007424B8 (en) * 2011-04-14 2014-04-10 Helmholtz-Zentrum Geesthacht Zentrum für Material- und Küstenforschung GmbH A process for producing a coating on the surface of a substrate based on light metals by plasma electrolytic oxidation and coated substrate
US8828215B2 (en) 2011-04-14 2014-09-09 Helmholtz-Zentrum Geesthacht Zentrum für Material-und Küstenforschung GmbH Process for producing a coating on the surface of a substrate based on lightweight metals by plasma-electrolytic oxidation

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