EP3307925B1 - Verfahren zur plasmaelektrolytischen oxidation - Google Patents

Verfahren zur plasmaelektrolytischen oxidation Download PDF

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Publication number: EP3307925B1
Authority: EP; European Patent Office
Prior art keywords: group containing; pulses; plasma; metallic particles; inorganic non
Prior art date: 2015-06-09
Legal status (The legal status 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 status listed.): Active

Application number

EP16732922.6A

Other languages

German (de)

English (en)

French (fr)

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EP3307925A1 (de

Inventor

Wolfgang Hansal

Selma Hansal

Rudolf Mann

Veronika GRMAN

Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

Hirtenberger Engineered Surfaces GmbH

Original Assignee

Hirtenberger Engineered Surfaces GmbH

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.)

2015-06-09

Filing date

2016-06-09

Publication date

2019-03-13

2016-06-09 Application filed by Hirtenberger Engineered Surfaces GmbH filed Critical Hirtenberger Engineered Surfaces GmbH

2018-04-18 Publication of EP3307925A1 publication Critical patent/EP3307925A1/de

2019-03-13 Application granted granted Critical

2019-03-13 Publication of EP3307925B1 publication Critical patent/EP3307925B1/de

Status Active legal-status Critical Current

2036-06-09 Anticipated expiration legal-status Critical

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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
- C25D11/024—Anodisation under pulsed or modulated current or potential
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/18—Electroplating using modulated, pulsed or reversing current
- 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
- C25D11/026—Anodisation with spark discharge
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
- 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
- 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
- C25D11/30—Anodisation of magnesium or alloys based thereon
- 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
- C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires

Definitions

the invention relates to a process for the plasma-electrolytic oxidation of workpieces made of light metal and / or light metal alloys containing a salt solution, wherein at least one salt or a combination of two or more salts is selected from a group comprising metal salts, in particular borates, phosphates, nitrates, sulfates, Aluminates, silicates, manganates, Molybdate, tungstates, and / or salts of organic acids, in particular methanesulfonates and / or amidosulfonates, and / or metal complexes and combinations thereof, wherein inorganic non-metallic particles are suspended in this salt solution.
metal salts in particular borates, phosphates, nitrates, sulfates, Aluminates, silicates, manganates, Molybdate, tungstates, and / or salts of organic acids, in particular methanesulfonates and / or amidosulf
An additional possibility for controlling the layer properties is the incorporation of particles which are dispersed in the electrolyte.
the incorporation of unmodified oxides, carbides and nitrides using alternating current is described in the article of VN Malyshev, KM Zorin, "Features of microarc oxidation coatings formation technologies in slurry electrolytes ", Appl. Surf. Sci. 254 (2007), 1511-1516 described.
a control of the superficial charge of the particles is possible in this method only on the pH of the electrolyte.
the plasma electrolytic oxidation process is possible only in certain pH ranges, which represents a significant limitation in the selection of the candidate particles.
a method of the type mentioned is in the DD 151 330 A1 described in which the production of diffusion layers by means of spark discharge is described in terms of fashion using equal and / or pulse voltage.
the inorganic non-metallic particles are surface-modified, wherein the inorganic non-metallic particles are surface-modified by means of reactive compounds selected from a group comprising silicon and / or germanium compounds, in particular germanium halides and / or siloxanes and / or contains halogenated silanes.
reactive compounds selected from a group comprising silicon and / or germanium compounds, in particular germanium halides and / or siloxanes and / or contains halogenated silanes.
the inorganic non-metallic particles are preferably selected from a group which contains insoluble oxides, hydroxides or silicates in the salt solution of the electrolyte.
the particles have an average diameter of at least 10 nm.
hydroxyl groups are chemically reactive and can be reacted, for example, with siloxanes according to the reaction scheme X-OH + (EtO) 3 Si-R ⁇ XO-Si (OEt) 2 -R (1) react.
X-OH + (EtO) 3 Si-R ⁇ XO-Si (OEt) 2 -R (1) react.
the chemical properties of the surface of the particles are changed such that the functional group of the siloxane determines the chemical surface properties.
This modification can be carried out both in an organic medium, such as toluene, and in aqueous solution.
This electrical surface charge can also be used to electrophoretically attach the particles to an oppositely charged electrode surface. Together with the plasma electrolytic oxidation, it is thus possible to store siloxane-modified particles in a plasma-electrolytically produced layer. This can be used, for example, to create higher layer thicknesses or to transfer certain properties of the particles (e.g., chemical composition or structural features) to the layer.
a positive charge is achieved, for example, by the use of siloxanes with amino groups, for example 3-aminopropyltrimethoxysilane.
the amino groups are protonated in an acidic medium, whereby the thus modified particle receives a positive surface charge.
3-mercaptopropyltrimethoxysiloxane and the subsequent oxidation to sulfonic acid according to the reaction equation R-SH + 3 H 2 O 2 ⁇ R-SO 3 H + 3 H 2 O (2) a negative surface charge in the neutral and basic medium can be achieved.
the modification of the surface on the one hand causes a high surface charge of the particles in the electrolyte in question to prevent precipitation
the particles can be transported electrophoretically to the electrode surface in the course of the deposition process. In this way, the incorporation rate of the particles in the resulting oxide layer can be controlled via the electrical parameters.
the inorganic non-metallic particles are selected from a group comprising clay minerals, in particular bentonite, kaolinite and / or montmorillonite. These Clay minerals naturally have a favorable surface energy or zeta potential, which leads to a stable electrolyte suspension.
the plasma-electrolytic oxidation takes place by means of direct current, in particular at a voltage of 250 V to 700 V. It is particularly preferred here that the current density is between 1 A / dm 2 and 30 A / dm 2 . Oxidation layers produced in this way have a particularly compact, dense layer which has only a very low porosity. Such a low porosity is particularly desirable when a particularly high corrosion resistance of the workpiece is required.
the plasma electrolytic oxidation is carried out by means of pulse methods, with anodic pulses preferably being applied at a voltage of 250 V to 700 V.
the current density be between 1 A / dm 2 and 30 A / dm 2 during the on fashionable pulses.
the use of the pulse method has the advantage that the plasma-chemical reaction at the surface of the workpiece can be controlled by targeted control of the pulses. This can be achieved in particular a small surface roughness and a lower porosity of the oxidation layer on the workpiece. Investigations by the applicant have also shown that a higher pulse frequency has a positive effect on the corrosion resistance of the coated workpieces.
additional cathodic pulses are applied whose voltage is preferably between 30 V and 200 V.
the current pulses have a duration of at least 5 ⁇ s and are separated by pauses of at least 3 ⁇ s.
the thickness and / or duration of the anodic and / or cathodic current pulses can also be varied during the production of the oxidation layer on the workpiece.
Aerosil 200 (a non-porous, amorphous silica having a specific surface area of 200 m 2 / g, Evonik Industries) were suspended in 1 l of n-butanol. Subsequently, a solution of 20 ml of 35% hydrochloric acid, 200 ml of 3-mercaptopropyltrimethoxysiloxane and 20 ml of water and a solution of 120 ml of 3-mercaptopropyltrimethoxysiloxane in 100 ml of n-butanol were added and the mixture was stirred at 40 ° C for 8 to 10 hours. Thereafter, a solution of 40 ml of 25% ammonia, 200 ml of 3-mercaptopropyltrimethoxysiloxane and 100 ml of n-butanol was added and the mixture was stirred overnight.
Aerosil 200 a non-porous, amorphous silica having a specific surface area of 200
modified Aerosil was taken up in 2 L of 35% H 2 O 2 and stirred at 60 ° C for 24 hours to oxidize the surface bound thiol groups to sulfonic acid.
the surface-modified Aerosil thus obtained was added to an electrolyte consisting of a solution of 3 g / l KOH and 3 g / l K 2 SiO 3 in a concentration of 30 g / l.
the substrate used was a 1 mm thick sheet of the industrially used 6082 aluminum alloy measuring 25 mm ⁇ 100 mm.
a bipolar rectangular pulse was used to produce the layer, the anodic and cathodic current density being 10 A / dm 2 and the respective pulse duration 500 ⁇ s, which corresponds to a frequency of 1 kHz.
the coating time was 30 minutes.
Figs. 1 and 3 and the associated EDX spectra according to the Figs. 2 and 4 show the formation of a compact, dense layer by the presence of the surface-modified particles in the electrolyte, which, in contrast to the particle-free layers produced only a low porosity.
Example 2 (not part of the claimed invention): Layer with bentonite
the substrate used was a 1 mm thick sheet of the copper-containing aluminum alloy 2017 with the dimensions 25 mm x 100 mm.
a bipolar rectangular pulse was used to produce the layer, the anodic and cathodic current density being 10 A / dm 2 and the respective pulse duration 500 ⁇ s, which corresponds to a frequency of 1 kHz.
the coating time was 30 minutes.

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Chemical & Material Sciences (AREA)
Engineering & Computer Science (AREA)
Chemical Kinetics & Catalysis (AREA)
Electrochemistry (AREA)
Materials Engineering (AREA)
Metallurgy (AREA)
Organic Chemistry (AREA)
Other Surface Treatments For Metallic Materials (AREA)

EP16732922.6A 2015-06-09 2016-06-09 Verfahren zur plasmaelektrolytischen oxidation Active EP3307925B1 (de)

Applications Claiming Priority (2)

Application Number	Priority Date	Filing Date	Title
ATA50467/2015A AT516503B1 (de)	2015-06-09	2015-06-09	Elektrolyt zur plasmaelektrolytischen oxidation
PCT/AT2016/050188 WO2016197175A1 (de)	2015-06-09	2016-06-09	Elektrolyt zur plasmaelektrolytischen oxidation

Publications (2)

Publication Number	Publication Date
EP3307925A1 EP3307925A1 (de)	2018-04-18
EP3307925B1 true EP3307925B1 (de)	2019-03-13

Family

ID=56097372

Family Applications (1)

Application Number	Title	Priority Date	Filing Date
EP16732922.6A Active EP3307925B1 (de)	2015-06-09	2016-06-09	Verfahren zur plasmaelektrolytischen oxidation

Country Status (5)

Country	Link
EP (1)	EP3307925B1 (da)
AT (1)	AT516503B1 (da)
DK (1)	DK3307925T3 (da)
ES (1)	ES2739548T3 (da)
WO (1)	WO2016197175A1 (da)

Cited By (2)

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Publication number	Priority date	Publication date	Assignee	Title
CN112301401A (zh) *	2020-10-29	2021-02-02	中国第一汽车股份有限公司	一种镁合金表面处理方法
EP3875636A1 (de)	2020-03-03	2021-09-08	RENA Technologies Austria GmbH	Verfahren zur plasmaelektrolytischen oxidation eines metallsubstrats

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
CN114657621B (zh) *	2020-12-24	2023-11-10	中国科学院上海硅酸盐研究所	一种提高镁合金表面微弧多孔氧化镁涂层抗腐蚀性的方法
CN113005498A (zh) *	2021-02-22	2021-06-22	佳木斯大学	一种自润滑锆基非晶合金及其制备方法和应用
CN114381778B (zh) *	2021-12-20	2023-12-01	中国兵器科学研究院宁波分院	一种镁及镁合金表面制备钽生物涂层的方法

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2015
- 2015-06-09 AT ATA50467/2015A patent/AT516503B1/de not_active IP Right Cessation
2016
- 2016-06-09 EP EP16732922.6A patent/EP3307925B1/de active Active
- 2016-06-09 DK DK16732922.6T patent/DK3307925T3/da active
- 2016-06-09 WO PCT/AT2016/050188 patent/WO2016197175A1/de not_active Ceased
- 2016-06-09 ES ES16732922T patent/ES2739548T3/es active Active

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
EP3875636A1 (de)	2020-03-03	2021-09-08	RENA Technologies Austria GmbH	Verfahren zur plasmaelektrolytischen oxidation eines metallsubstrats
WO2021175868A1 (de)	2020-03-03	2021-09-10	RENA Technologies Austria GmbH	Verfahren zur plasmaelektrolytischen oxidation eines metallsubstrats
CN112301401A (zh) *	2020-10-29	2021-02-02	中国第一汽车股份有限公司	一种镁合金表面处理方法
CN112301401B (zh) *	2020-10-29	2022-01-14	中国第一汽车股份有限公司	一种镁合金表面处理方法

Also Published As

Publication number	Publication date
WO2016197175A1 (de)	2016-12-15
DK3307925T3 (da)	2019-06-24
AT516503B1 (de)	2016-06-15
ES2739548T3 (es)	2020-01-31
EP3307925A1 (de)	2018-04-18
AT516503A4 (de)	2016-06-15

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