EP3307925A1 - Elektrolyt zur plasmaelektrolytischen oxidation - Google Patents
Elektrolyt zur plasmaelektrolytischen oxidationInfo
- Publication number
- EP3307925A1 EP3307925A1 EP16732922.6A EP16732922A EP3307925A1 EP 3307925 A1 EP3307925 A1 EP 3307925A1 EP 16732922 A EP16732922 A EP 16732922A EP 3307925 A1 EP3307925 A1 EP 3307925A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- electrolyte
- electrolytic oxidation
- plasma
- light metal
- pulses
- Prior art date
- 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.)
- Granted
Links
- 239000003792 electrolyte Substances 0.000 title claims abstract description 28
- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 239000013528 metallic particle Substances 0.000 claims abstract description 11
- 229910001092 metal group alloy Inorganic materials 0.000 claims abstract description 7
- 150000004760 silicates Chemical class 0.000 claims abstract description 6
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 3
- 150000004645 aluminates Chemical class 0.000 claims abstract description 3
- 150000001642 boronic acid derivatives Chemical class 0.000 claims abstract description 3
- AFVFQIVMOAPDHO-UHFFFAOYSA-M methanesulfonate group Chemical class CS(=O)(=O)[O-] AFVFQIVMOAPDHO-UHFFFAOYSA-M 0.000 claims abstract description 3
- 150000002823 nitrates Chemical class 0.000 claims abstract description 3
- 150000007524 organic acids Chemical class 0.000 claims abstract description 3
- 235000005985 organic acids Nutrition 0.000 claims abstract description 3
- 235000021317 phosphate Nutrition 0.000 claims abstract description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims abstract description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims abstract description 3
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 239000000440 bentonite Substances 0.000 claims description 6
- 229910000278 bentonite Inorganic materials 0.000 claims description 6
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 6
- -1 germanium halides Chemical class 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 239000002734 clay mineral Substances 0.000 claims description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- 150000002291 germanium compounds Chemical class 0.000 claims description 2
- 150000004679 hydroxides Chemical class 0.000 claims description 2
- CYPPCCJJKNISFK-UHFFFAOYSA-J kaolinite Chemical compound [OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[O-][Si](=O)O[Si]([O-])=O CYPPCCJJKNISFK-UHFFFAOYSA-J 0.000 claims description 2
- 229910052622 kaolinite Inorganic materials 0.000 claims description 2
- 229910001234 light alloy Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000004756 silanes Chemical class 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims 2
- 239000000956 alloy Substances 0.000 claims 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 1
- 229910052790 beryllium Inorganic materials 0.000 claims 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- 229910052715 tantalum Inorganic materials 0.000 claims 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims 1
- 229910052726 zirconium Inorganic materials 0.000 claims 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract 2
- 239000002245 particle Substances 0.000 description 18
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000000576 coating method Methods 0.000 description 5
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000010348 incorporation Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 229910002016 Aerosil® 200 Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910003849 O-Si Inorganic materials 0.000 description 1
- 229910003872 O—Si Inorganic materials 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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 an electrolyte for the plasma-electrolytic oxidation of workpieces produced from light metal and / or light alloys, comprising 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, manganites, molybdate, tungstates, and / or salts of organic acids, in particular methanesulfonates and / or amidosulfonates, and / or metal complexes and combinations thereof, and a method for this purpose.
- metal salts in particular borates, phosphates, nitrates, sulfates, Aluminates, silicates, manganites, molybdate, tungstates, and / or salts of organic acids, in particular methanesulfonates and / or amidosulfonates, and / or
- 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 by VN Malyshev, KM Zorin, "Features of microarc oxidation coatings formation technologies in slurry electrolytes", Appl. Surf. Be. 254 (2007), 1511-1516.
- a control of the superficial charge of In this process particles are only possible via 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.
- inorganic non-metallic particles are suspended in this salt solution.
- 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 inorganic non-metallic particles have an average diameter of at least 10 nm, and are preferably surface-modified, so that their surface energy and / or zeta potential is increased or reduced in terms of their initial state.
- Such a surface modification causes the inorganic non-metallic particles to be uniformly suspended in the electrolyte, allowing uniform incorporation into the oxidation layer during the deposition process.
- hydroxyl groups are chemically reactive and can be reacted, for example, with siloxanes according to the reaction scheme
- This modification can be carried out both in an organic medium, such as toluene, and in aqueous solution.
- a positive charge is achieved, for example, by the use of siloxanes having amino groups, e.g. 3-aminopropyltrimethoxysilane achieved.
- 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 0 2 - "a negative surface charge can be achieved in neutral and basic media ⁇ R-SO3H + 3H 2 0 (2).
- 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, on the other hand, 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 invention furthermore relates to a process for the plasma-electrolytic oxidation of workpieces produced from light metal and / or light metal alloys with an electrolyte according to the invention described above.
- 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 makes it possible, in particular, to achieve a low 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 ⁇ and are separated by pauses of at least 3 ⁇ .
- 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.
- FIG. 1 shows a scanning electron micrograph of the surface of a surface-modified SiO 2 particles produced PEO layer.
- FIG. 2 shows the EDX spectrum of the surface of FIG. 1;
- FIG. 3 shows a scanning electron micrograph of a cross section through the PEO layer from FIG. 1;
- FIG. 5 shows a scanning electron micrograph of the surface of a PEO layer produced with bentonite additive
- FIG. 6 shows the EDX spectrum of the surface of FIG. 5;
- FIG. 7 is a scanning electron micrograph of a cross section through the PEO layer of FIG. 5; FIG.
- Fig. 8 shows the EDX spectrum of a cross section of the PEO layer
- 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 in order to oxidise the surface-bonded thiol groups to sulfonic acid.
- the thus-obtained surface-modified Aerosil was added to an electrolyte consisting of a solution of 3 g / L KOH and 3 g / L K 2 S 13 O 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 MS, which corresponds to a frequency of 1 kHz.
- the coating time was 30 minutes.
- the scanning electron images according to FIGS. 1 and 3 and the associated EDX spectra according to FIGS. 2 and 4 show the formation of a compact, dense layer due to the presence of the surface-modified particles in the electrolyte, which in contrast to the particle-free produced layers only one has low porosity.
- Example 2 Layer with bentonite a. ) Preparation of the electrolyte
- 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 ⁇ , which corresponds to a frequency of 1 kHz.
- the coating time was 30 minutes.
Landscapes
- 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)
Abstract
Description
Claims
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 true EP3307925A1 (de) | 2018-04-18 |
EP3307925B1 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 (de) |
AT (1) | AT516503B1 (de) |
DK (1) | DK3307925T3 (de) |
ES (1) | ES2739548T3 (de) |
WO (1) | WO2016197175A1 (de) |
Families Citing this family (5)
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 |
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 |
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 |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DD151330A1 (de) * | 1980-06-03 | 1981-10-14 | Peter Kurze | Verfahren zur herstellung von diffusionsschichten in metallen |
DE19912502A1 (de) * | 1999-03-19 | 2000-09-21 | Inst Neue Mat Gemein Gmbh | Nanoskalige Teilchen, Komplexe mit Polynukleotiden und deren Verwendung |
GB0126467D0 (en) * | 2001-11-03 | 2002-01-02 | Accentus Plc | Deposition of coatings on substrates |
GB2386907B (en) * | 2002-03-27 | 2005-10-26 | Isle Coat Ltd | Process and device for forming ceramic coatings on metals and alloys, and coatings produced by this process |
CN101555597A (zh) * | 2009-05-13 | 2009-10-14 | 大连理工大学 | 一种镍钛合金表面氧化钛生物活性涂层的制备方法 |
KR101067743B1 (ko) * | 2009-11-18 | 2011-09-28 | 한국생산기술연구원 | 마그네슘 또는 마그네슘 합금의 양극산화 표면 처리 방법 |
US8888982B2 (en) * | 2010-06-04 | 2014-11-18 | Mks Instruments Inc. | Reduction of copper or trace metal contaminants in plasma electrolytic oxidation coatings |
EA201390661A1 (ru) * | 2011-02-08 | 2014-04-30 | Кембридж Нанолитик Лимитед | Неметаллическое покрытие и способ его создания |
DE102011007424B8 (de) * | 2011-04-14 | 2014-04-10 | Helmholtz-Zentrum Geesthacht Zentrum für Material- und Küstenforschung GmbH | Verfahren zur Herstellung einer Beschichtung auf der Oberfläche eines Substrats auf Basis von Leichtmetallen durch plasmaelektrolytische Oxidation und beschichtetes Substrat |
US8808522B2 (en) * | 2011-09-07 | 2014-08-19 | National Chung Hsing University | Method for forming oxide film by plasma electrolytic oxidation |
KR101433832B1 (ko) * | 2013-02-04 | 2014-08-26 | 조호현 | 내식성을 강화한 마그네슘 케로나이트 방법 |
-
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 ES ES16732922T patent/ES2739548T3/es active Active
- 2016-06-09 WO PCT/AT2016/050188 patent/WO2016197175A1/de unknown
- 2016-06-09 DK DK16732922.6T patent/DK3307925T3/da active
Also Published As
Publication number | Publication date |
---|---|
AT516503A4 (de) | 2016-06-15 |
WO2016197175A1 (de) | 2016-12-15 |
ES2739548T3 (es) | 2020-01-31 |
DK3307925T3 (da) | 2019-06-24 |
AT516503B1 (de) | 2016-06-15 |
EP3307925B1 (de) | 2019-03-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP3307925B1 (de) | Verfahren zur plasmaelektrolytischen oxidation | |
DE102008043682B4 (de) | Verfahren zum Beschichten von metallischen Oberflächen mit Partikeln, nach diesem Verfahren hergestellte Beschichtung und Verwendungder nach diesem Verfahren beschichteten Substrate | |
US8828215B2 (en) | Process for producing a coating on the surface of a substrate based on lightweight metals by plasma-electrolytic oxidation | |
EP3414355B1 (de) | Aluminiumbasierte beschichtung für stahlbleche oder stahlbänder und verfahren zur herstellung hierzu | |
Saji | Electrophoretic‐deposited superhydrophobic coatings | |
WO2011067094A1 (de) | Mehrstufiges vorbehandlungsverfahren für metallische bauteile mit zink- und eisenoberflächen | |
WO2000056950A2 (de) | Chemisch passivierter gegenstand aus magnesium oder seinen legierungen | |
DE102010062357B4 (de) | Vorrichtung und Verfahren zur Herstellung eines mit zumindest einer Korrosionsschutzschicht beschichteten magnesiumhaltigen Substrats | |
EP1394292A2 (de) | Elektrochemisch erzeugte TiO2-Schichten zum Korrosionsschutz oder als Haftgrund | |
EP3455301B1 (de) | Korrosionsschutz | |
DE102014211386B3 (de) | Verfahren zur Beschichtung eines Substrats | |
WO2009141150A1 (de) | Beschichtete substrate und verfahren zu deren herstellung | |
DE10163743B4 (de) | Beschichteter Gegenstand aus Stahl, Verfahren zu seiner Herstellung und seine Verwendung | |
DE102006035974A1 (de) | Verfahren zur Phosphatierung einer Metallschicht | |
EP1433879B1 (de) | Verfahren zur Beschichtung von Metalloberflächen mit einer Alkaliphosphatierungslösung, wässeriges Konzentrat und Verwendung der derart beschichteten Metalloberflächen | |
DE102007008877A1 (de) | Bariumsulfat | |
DE102017011379A1 (de) | Anti-Korrosionsbeschichtung für metallische Substrate | |
WO2016174122A1 (de) | Verfahren zur versieglung von oxidischen schutzschichten auf metallsubstraten | |
WO2017088982A1 (de) | Verfahren zum herstellen einer metalloberfläche | |
DE102017103602A1 (de) | Beschichtung eines Werkstoffes und Verfahren zu deren Erzeugung sowie Werkstück |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20180109 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
DAV | Request for validation of the european patent (deleted) | ||
DAX | Request for extension of the european patent (deleted) | ||
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
INTG | Intention to grant announced |
Effective date: 20181114 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE PATENT HAS BEEN GRANTED |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D Free format text: NOT ENGLISH |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP Ref country code: AT Ref legal event code: REF Ref document number: 1107773 Country of ref document: AT Kind code of ref document: T Effective date: 20190315 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Free format text: LANGUAGE OF EP DOCUMENT: GERMAN |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 502016003762 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: DK Ref legal event code: T3 Effective date: 20190617 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: FP |
|
REG | Reference to a national code |
Ref country code: SE Ref legal event code: TRGR |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190613 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190313 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190313 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R082 Ref document number: 502016003762 Country of ref document: DE Representative=s name: LS-MP VON PUTTKAMER BERNGRUBER LOTH SPUHLER MU, DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190613 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190313 Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190313 Ref country code: RS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190313 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190614 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: NV Representative=s name: SCHMAUDER AND PARTNER AG PATENT- UND MARKENANW, CH |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190313 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190313 Ref country code: AL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190313 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190313 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190313 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190713 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190313 Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190313 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 502016003762 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190713 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190313 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2739548 Country of ref document: ES Kind code of ref document: T3 Effective date: 20200131 |
|
26N | No opposition filed |
Effective date: 20191216 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190313 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20190609 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20190609 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R082 Ref document number: 502016003762 Country of ref document: DE Representative=s name: LS-MP VON PUTTKAMER BERNGRUBER LOTH SPUHLER MU, DE Ref country code: DE Ref legal event code: R081 Ref document number: 502016003762 Country of ref document: DE Owner name: RENA TECHNOLOGIES AUSTRIA GMBH, AT Free format text: FORMER OWNER: HIRTENBERGER ENGINEERED SURFACES GMBH, HIRTENBERG, AT |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190313 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: PC Ref document number: 1107773 Country of ref document: AT Kind code of ref document: T Owner name: RENA TECHNOLOGIES AUSTRIA GMBH, AT Effective date: 20210416 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190313 Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO Effective date: 20160609 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20210630 Year of fee payment: 6 Ref country code: NL Payment date: 20210621 Year of fee payment: 6 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 20210623 Year of fee payment: 6 Ref country code: DK Payment date: 20210623 Year of fee payment: 6 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190313 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20210722 Year of fee payment: 6 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190313 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20220623 Year of fee payment: 7 Ref country code: DE Payment date: 20220621 Year of fee payment: 7 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20220621 Year of fee payment: 7 Ref country code: AT Payment date: 20220622 Year of fee payment: 7 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20220622 Year of fee payment: 7 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 20220629 Year of fee payment: 7 |
|
REG | Reference to a national code |
Ref country code: DK Ref legal event code: EBP Effective date: 20220630 |
|
REG | Reference to a national code |
Ref country code: SE Ref legal event code: EUG |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: MM Effective date: 20220701 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20220701 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20220610 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20230728 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20220609 Ref country code: DK Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20220630 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20220610 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 502016003762 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MM01 Ref document number: 1107773 Country of ref document: AT Kind code of ref document: T Effective date: 20230609 |
|
REG | Reference to a national code |
Ref country code: BE Ref legal event code: MM Effective date: 20230630 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20230609 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20230609 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20240103 Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20230609 Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20230609 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20230630 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20230630 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20230630 |