WO2016190737A2 - Procédé de production de zones isolées ou électriquement isolées dans un métal et produit comprenant une telle zone - Google Patents

Procédé de production de zones isolées ou électriquement isolées dans un métal et produit comprenant une telle zone Download PDF

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Publication number
WO2016190737A2
WO2016190737A2 PCT/NL2016/050372 NL2016050372W WO2016190737A2 WO 2016190737 A2 WO2016190737 A2 WO 2016190737A2 NL 2016050372 W NL2016050372 W NL 2016050372W WO 2016190737 A2 WO2016190737 A2 WO 2016190737A2
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WO
WIPO (PCT)
Prior art keywords
metallic structure
metal
metallic
layer
product
Prior art date
Application number
PCT/NL2016/050372
Other languages
English (en)
Other versions
WO2016190737A3 (fr
Inventor
Sybrandus Jacob Metz
Hans Hendrik Wolters
Johannes Kuipers
Original Assignee
Metalmembranes.Com B.V.
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 Metalmembranes.Com B.V. filed Critical Metalmembranes.Com B.V.
Priority to EP16747634.0A priority Critical patent/EP3303661A2/fr
Priority to US15/576,203 priority patent/US20180142373A1/en
Priority to CN201680043380.4A priority patent/CN107923061A/zh
Publication of WO2016190737A2 publication Critical patent/WO2016190737A2/fr
Publication of WO2016190737A3 publication Critical patent/WO2016190737A3/fr

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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
    • C25D11/022—Anodisation on selected surface areas
    • 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
    • C25D11/18—After-treatment, e.g. pore-sealing
    • C25D11/20—Electrolytic after-treatment
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F3/00—Electrolytic etching or polishing
    • C25F3/02—Etching
    • C25F3/04—Etching of light metals

Definitions

  • the present invention relates to a method to produce electrically isolated or insulated areas in a metal. Such areas are used in various applications, including electronic devices. More specifically, the method according to the invention relates to forming metal structures that have an electrically isolated area that is connected by non-conductive part(s). In this context isolating and insulating both describe the electrical separation of an area from other parts and can be used alternately in the context of the present invention.
  • the present invention has for its object to improve conventional products having an electrically isolated area.
  • the treated structure can be used in various applications, including electronic devices. More specifically, the method according to the invention relates to forming metal structures that have an electrically isolated area that is connected by non-conductive part(s). Such structure can advantageously be used as an antenna or antenna part, such as an RF antenna. Such antenna that is produced involving the method according to the present invention enables improved
  • the ceramic layer has a thickness in the range of 5-300 ⁇ , preferably 10-200 ⁇ , more preferably 15-150 ⁇ and most preferably a thickness is about 100 um.
  • the ceramic layer By providing the ceramic layer with a sufficient thickness the stability and strength of the heater is improved. Furthermore, the insulation is increased, enabling control of heat transfer and/or heat production.
  • the thickness of the ceramic layer is preferably adapted to the desired characteristics. This flexibility during production provides a further advantage of the system according to the invention.
  • the ceramic layer is provided on or at the conductor with plasma electrolytic oxidation (PEO).
  • the element is preferably made from an aluminium material, or other suitable material, such as titanium, on which a porous metal oxide layer, such as aluminium oxide or titanium oxide, is grown with plasma electrolytic oxidation.
  • the metal oxide layer is provided on a side of the metal layer involving a plasma oxidation process, more specifically a plasma electrolytic oxidation process.
  • the plasma electrolytic oxidation process creates very fine pores in the metal layer, thereby forming an oxide layer that contains small pores.
  • This method provides a ceramic layer that can be made efficiently. Surprisingly, also the pore sizes of this ceramic layer can be controlled more effectively and the desired characteristics for such ceramic layer can be achieved more accurately.
  • a further advantage of the method according to the invention is that it enables the manufacturing of ceramic material in a modular way. Optionally, this enables providing complicated three-dimensional shapes of the desired element.
  • Plasma electrolytic oxidation enables that a relatively thick aluminium, titanium or other suitable metal layer is grown from the metal (>130 ⁇ ) by oxidizing (part of) the metal to metal oxide. Especially the use of titanium provides good results.
  • the resulting layer is a porous, flexible and elastic metal oxide ceramic.
  • Plasma electrolytic oxidation (>350 - 550 V) requires much higher voltage compared to standard anodizing (15-21 V). At this high voltage, micro discharge arcs appear on the surface of the aluminium, or other material, and cause the growth of the thick (metal) oxide layer. Results have shown that a ceramic layer can be achieved on an aluminium foil of about 13 ⁇ thickness, with a flexible and elastic ceramic layer.
  • One of the advantageous effects of using plasma electrolytic oxidation to provide the ceramic layer is that due to the growth of the layer from the metal during oxidation the adherence of the ceramic layer to the metal is excellent.
  • Alternative manufacturing methods for producing an electrically isolated area in a metal include sintering or spark plasma sintering, oxidation of the surface layer of the metal by heating in oxygen rich environment, anodizing, and plasma spraying. Also, it would be possible to deposit an aluminium, or other material, coating on the conductor of the heater element, for example with arc spraying, and to oxidize the deposited material to an oxide with plasma electrolytic oxidation.
  • an anodization process may be applied to provide a ceramic layer.
  • anodization takes place at a voltage that from 1 to 300 V DC, although most fall in the range of 15 to 21 V. Higher voltages are typically required for thicker coatings formed in sulfuric and organic acid.
  • the current that is applied is in the range from 30 to 300 amperes/meter 2 .
  • the resulting ceramic layer may has pores with a diameter in the range of 1-150 nm in diameter on the interface of the metal/ceramic layer and has pores with a diameter in the range of 50 nm to 5 ⁇ on the outside.
  • the ceramic layer thickness can range from under 0.5 ⁇ up to 150 ⁇ for architectural applications.
  • the method comprises the step of electrically isolating a part of the metallic structure by removing part of the metallic structure. This provides separate parts/elements in the metallic structure that are electrically isolated.
  • the method in another presently preferred embodiment of the invention comprises the step of connecting a further metallic structure to the metallic structure with the oxide layer. Because of the process conditions, involving high temperatures and pressure, the metal oxide layer melts during plasma oxidation and solidifies again during cooling. Provided the further metallic structure is positioned closed to the metallic structure the oxide layers of the respective structure will solidify together, thereby connecting the metallic structures, while preferably electrically isolating the metallic structures.
  • the method further comprises the step of masking parts of the metallic structure and performing the plasma electrolytic oxidation and/or anodization such that an oxide layer is achieved on an unmasked area of the metallic structure.
  • removing part of the metallic structure is performed after performing the plasma electrolytic oxidation process. This enables effective oxidation. More preferably, removing part of the metallic structure comprises performing an etching process, for example chemical etching or electrochemical etching.
  • the etching involves electrochemical etching.
  • Electrochemical etching also referred to as electrochemical machining (ECM) and preferably including jet electrochemical machining (JET-ECM), allows for a precise, fast and reproducible local removal of material of the first metal layer.
  • ECM electrochemical machining
  • JET-ECM jet electrochemical machining
  • etching the first metal layer does not significantly influence the metal oxide layer.
  • the metal oxide layer remains substantially intact whereas the metal is locally etched away.
  • This enables an efficient and effective manufacturing of a product comprising an electrically isolated area, for example.
  • Performing the removing step after producing the oxide layer further improves the electric isolation of the respective area. For example, this may prevent or reduce undesired bulging and/or oxidation to the sides in a transversal direction. This improves the quality of the resulting product. Also, this may further reduce the noise disturbance.
  • the etching process that is applied may automatically stop when reaching the oxide layer. This improves the isolation that is effectively provided.
  • the method further comprises the step of providing non-conductive material to the removed areas of the metallic structures.
  • the method further comprises the step of increasing the stability and/or strength of the metallic structure by providing a stability layer on the oxide layer of the metallic structure after performing the plasma electrolytic oxidation and/or anodization process.
  • the stability layer By providing a stability layer the strength and stability of the metallic structure is significantly improved. This improves the etching performance.
  • the stability layer comprises non-conductive material, for example an epoxy.
  • the stability layer is provided with a thickness in the range of 10 to 100 ⁇ , preferably in the range of 20 to 75 ⁇ , and most preferably with a thickness of about 50 ⁇ . It was shown that such thickness improves stability and strength thereby enabling or improving possibilities for further processing, such as electrochemical etching.
  • the method further comprises the step of removing the stability layer.
  • the stability layer is removed after performing the etching process. This may depend on the actual use or application of the product.
  • the method further comprises the step of providing a third metallic structure connecting the other metallic structures together.
  • such third metallic structure will connect the two other metallic structures together in preferably a plasma oxidation process.
  • at least one of the two, three of further metallic structures is of a different material.
  • the third metallic structure is a sacrificial metallic structure that can be used to connect the other metallic structures.
  • An example of such embodiment is the use of a titanium structure as third, sacrificial structure for connecting two aluminum structures.
  • metallic structures of aluminum, magnesium and titanium are connected together.
  • the present invention also relates to a product according to the invention, with the product comprising an electrically isolated area that is produced with a method as described earlier.
  • such product is a computing device, such as mobile phones, tablets, computers, laptops etc., and the area is part of an antenna.
  • the effects of undesired noise in the communication can be significantly reduced.
  • the product may have different shapes or configurations.
  • the metallic structures of the product may comprise a tubular shape, a metallic mesh structure on the metallic structure, or a wire shape.
  • Figure 1 shows a cell and metal that is subjected to plasma oxidation according to the present invention
  • Figure 2 shows a cross section of the product resulting from the method according to the invention
  • Figure 3 shows a top view of the product shown in figure 2;
  • Figure 4 shows a process according to an embodiment of the invention with a stability layer
  • Figure 5 A-D shows different embodiments of the invention with two or more metallic structures.
  • a piece of metal 2 (figure 1) is subjected to plasma oxidation to create an oxide layer 4 on a metal plate.
  • the metal is placed in a plasma electrolytic oxidation cell 6 as shown in figure 1.
  • the metal plate 2 preferably aluminum is connected to an anode.
  • Alternative materials titanium, magnesium or other so called valve metals can also be used.
  • the synthetic material 8 shown in the figure can be a hard plastic which can be compressed against another hard plastic with in between a metal plate 2 and a rubber 10 for sealing. This synthetic material 8 acts as a masking material to form plasma electrolytic oxide 4 at unmasked areas 12. Different kind of shapes can be used to mask the metal plate 2.
  • the rubber material 10 seals the cell and masks the metal 2.
  • the synthetic material 8 also acts as a mask. In such a cell 6 as described here only the part 12 which is not masked is treated through plasma electrolytic oxidation.
  • Plasma electrolytic oxidation (PEO) or micro arc oxidation creates a non-conductive metal oxide layer 4 on the metal plate 2.
  • PEO Plasma electrolytic oxidation
  • Electrolytes that can be used contain KOH (potassium hydroxide) in a concentration range 0 - 10 g/1, and Na 2 Si0 3 5H 2 0 concentration range 0-10 g/1, for example.
  • the structure of the metal element 2 comprises a thin plate or sheet of titanium, aluminium, or any other valve metal, such as magnesium, zirconium, zinc, niobium, vanadium, hafnium, tantalum, molybdenum, tungsten, antimony, bismuth, or an alloy of one or more of the preceding metals.
  • Plate or sheet 2 is coated on the other side through plasma electrolytic oxidation.
  • Plasma electrolytic oxidation is done by placing titanium plate or sheet 2 in an electrolyte.
  • the electrolyte comprises 15 g/1 (NaP0 3 ) 6 and 8 g/1 Na 2 Si0 3 .5H 2 0. The electrolyte is maintained at a temperature of 25°C through cooling.
  • Plate or sheet 2 is used as an anode and placed in a container containing the electrolyte.
  • a stainless steel cathode 12 is positioned around plate or sheet 2 .
  • a current density is maintained between the plate or sheet and cathode 22 of about 0.15 A/cm 2 .
  • the current is applied in a pulsed mode of about 1000 Hz.
  • the current increases rapidly to about 500 Volt between the plate or sheet and cathode 22. This creates a plasma electrolytic oxidation process on anode plate or sheet 2 and creates ceramic layer 4. It will be understood that process parameters may depend on the structure of the plate or sheet and/or the dimensions thereof.
  • a ceramic layer 4 is obtained with a layer thickness that depends on the treatment time.
  • the metal 14 remaining attached to the ceramic layer 4 has to be removed.
  • Electrochemical machining is very effective in removing the metal 14 under the oxide layer 4 and is a presently preferred embodiment of the present invention.
  • the metal plate was transferred to an etch cell.
  • the metal was etched via electrochemical machining.
  • the plate was mounted in this cell with the metal side facing the cathode.
  • This cathode consists partly of a metal and a plastic.
  • the metal shape of the cathode determines the shape and dimensions which will be etched in the metal plate.
  • a pulsed electric field is applied between the cathode and the anode (metal plate with on the other side the metal oxide layer).
  • a highly conductive electrolytic flow was provided between the anode and the cathode. The potential difference between the anode and the cathode was in the beginning 10 - 15 Volts and increased gradually during the etching.
  • This process results in a metal plate with on one side a metal oxide layer and a structure etched in the metal. Fluids can be filtrated through the open structure in the metal.
  • the metal oxide layer can be supported during filtration by a metal plate and/or a (paper) filter that is optionally provided in between the metal oxide layer and the metal plate. Because the surface roughness of the metal oxide layer is high the permeate water can flow easily away to the sides and can be separated from the feed water. This filtration configuration also allows for high filtration pressures over 5 bars. Tests have shown that a combination of the PEO process with electrochemical machining achieves a high quality product, for example with very accurate removal of the metal at the desired spots.
  • part of the metal 14 can be removed from the other side by electrochemical machining, for example.
  • electrochemical machining is that the process stops when it reaches the non-conductive ceramic layer 4.
  • the formed opening can be filled with a non-conductive polymer 16 or other substances. By doing so, electrically isolated areas 18 are created.
  • a cross section of a product 20 formed this way is shown in figure 2.
  • a top view of product 20 may look like as shown in figure 3.
  • manufacturing process 102 starts with providing metal plate of sheet 104.
  • ceramic layer 106 is provided on one side of metal element 104.
  • stability layer 108 is provided on and/or in ceramic layer 106 to improve stability and strength of element 104 with ceramic layer 106.
  • stability layer 108 is from epoxy.
  • an ECM process is performed that provides grooves, holes or openings 110 from the other side of element 104. The ECM process is stopped as grooves, holes or openings 110 reach ceramic layer 106.
  • grooves, holes or openings 110 are filled with non-conductive material 112, for example epoxy.
  • stability later 108 can be removed from ceramic layer 106.
  • metallic structure 204 is connected to second metallic structure 206 with plasma electrolytic oxidation bonding metallic structures 204, 206 together with the oxide layers.
  • the connection is made such that metallic structures 204, 206 are electrically isolated.
  • two metallic structures 210, 212 are connected with sacrificial third metallic structure 214.
  • the respective materials for metallic structures 210, 212 and 214 are aluminum, magnesium and titanium.
  • middle structure 214 is of titanium and the other structures 210, 212 are of aluminum.
  • the structures can be shaped as plates or sheets. Alternatively, other shapes are possible.
  • process 216 (figure 5C) two tubular metallic structures 218, 220 are connected. Such shape may act as antenna, for example.
  • mesh 224 (or alternatively a wire) is connected to plate/sheet 226 (or alternatively a wire). Also, two or more wires may be connected.
  • shapes or configurations can be envisaged in accordance with the invention. All different kind of shapes can be made on the metal by plasma electrolytic oxidation and masking the metal during plasma oxidation and removing the metal after plasma oxidation by electrochemical machining and filling the cavity with a nonconductive material.

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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)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
  • Plasma Technology (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)

Abstract

La présente invention concerne un procédé pour produire des zones isolées ou électriquement isolées dans un métal, et un produit comprenant une telle zone. Le procédé selon l'invention comprend les étapes consistant à : - fournir une structure métallique ; - effectuer un processus d'anodisation et/ou d'oxydation électrolytique au plasma de telle sorte qu'une couche d'oxyde est réalisée sur une zone de la structure métallique ; et - isoler électriquement une partie de la structure métallique par le retrait d'une partie de la structure métallique et/ou la liaison d'une autre structure métallique à la structure métallique avec la couche d'oxyde.
PCT/NL2016/050372 2015-05-26 2016-05-25 Procédé de production de zones isolées ou électriquement isolées dans un métal et produit comprenant une telle zone WO2016190737A2 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP16747634.0A EP3303661A2 (fr) 2015-05-26 2016-05-25 Procédé de production de zones isolées ou électriquement isolées dans un métal et produit comprenant une telle zone
US15/576,203 US20180142373A1 (en) 2015-05-26 2016-05-25 Method to produce electrically isolated or insulated areas in a metal, and a product comprising such area
CN201680043380.4A CN107923061A (zh) 2015-05-26 2016-05-25 在金属中产生电隔离或绝缘区域的方法以及包括这种区域的产品

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL2014857 2015-05-26
NL2014857 2015-05-26

Publications (2)

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WO2016190737A2 true WO2016190737A2 (fr) 2016-12-01
WO2016190737A3 WO2016190737A3 (fr) 2017-02-09

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PCT/NL2016/050372 WO2016190737A2 (fr) 2015-05-26 2016-05-25 Procédé de production de zones isolées ou électriquement isolées dans un métal et produit comprenant une telle zone

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US (1) US20180142373A1 (fr)
EP (1) EP3303661A2 (fr)
CN (1) CN107923061A (fr)
WO (1) WO2016190737A2 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170121840A1 (en) * 2015-10-30 2017-05-04 Essential Products, Inc. Methods of manufacturing structures having concealed components
US9882275B2 (en) 2015-10-30 2018-01-30 Essential Products, Inc. Antennas for handheld devices
US10158164B2 (en) 2015-10-30 2018-12-18 Essential Products, Inc. Handheld mobile device with hidden antenna formed of metal injection molded substrate

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011010914A1 (fr) 2009-07-20 2011-01-27 Metal Membranes.Com B.V. Procédé de production d'une membrane et membrane ainsi produite

Family Cites Families (4)

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Publication number Priority date Publication date Assignee Title
FR2466103A1 (fr) * 1979-09-18 1981-03-27 Lerouzic Jean Procede de realisation d'un reseau d'interconnexion de composants electroniques a conducteurs en aluminium et isolant en alumine et reseau d'interconnexion obtenu par ce procede
KR100601506B1 (ko) * 2004-08-24 2006-07-19 삼성전기주식회사 양극 산화에 의한 미세 회로패턴이 형성된 패키지 기판의제조 방법
US8890409B2 (en) * 2008-05-14 2014-11-18 The Board Of Trustees Of The University Of Illnois Microcavity and microchannel plasma device arrays in a single, unitary sheet
JP5373745B2 (ja) * 2010-11-05 2013-12-18 幸子 小野 エッチング特性に優れた電解コンデンサ電極用アルミニウム材の製造方法、アルミニウム電解コンデンサ用電極材ならびにアルミニウム電解コンデンサ

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011010914A1 (fr) 2009-07-20 2011-01-27 Metal Membranes.Com B.V. Procédé de production d'une membrane et membrane ainsi produite

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170121840A1 (en) * 2015-10-30 2017-05-04 Essential Products, Inc. Methods of manufacturing structures having concealed components
US9882275B2 (en) 2015-10-30 2018-01-30 Essential Products, Inc. Antennas for handheld devices
US9896777B2 (en) 2015-10-30 2018-02-20 Essential Products, Inc. Methods of manufacturing structures having concealed components
US10158164B2 (en) 2015-10-30 2018-12-18 Essential Products, Inc. Handheld mobile device with hidden antenna formed of metal injection molded substrate

Also Published As

Publication number Publication date
CN107923061A (zh) 2018-04-17
EP3303661A2 (fr) 2018-04-11
WO2016190737A3 (fr) 2017-02-09
US20180142373A1 (en) 2018-05-24

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