EP2010699A2 - Dispositif et procédé de revêtement galvanique - Google Patents
Dispositif et procédé de revêtement galvaniqueInfo
- Publication number
- EP2010699A2 EP2010699A2 EP07728172A EP07728172A EP2010699A2 EP 2010699 A2 EP2010699 A2 EP 2010699A2 EP 07728172 A EP07728172 A EP 07728172A EP 07728172 A EP07728172 A EP 07728172A EP 2010699 A2 EP2010699 A2 EP 2010699A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- substrate
- electrically conductive
- conductive
- band
- waves
- 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.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/10—Electrodes, e.g. composition, counter electrode
- C25D17/14—Electrodes, e.g. composition, counter electrode for pad-plating
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/005—Contacting devices
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/10—Electrodes, e.g. composition, counter electrode
- C25D17/12—Shape or form
-
- 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
- C25D5/04—Electroplating with moving electrodes
- C25D5/06—Brush or pad plating
-
- 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
- C25D5/54—Electroplating of non-metallic surfaces
-
- 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
- C25D5/54—Electroplating of non-metallic surfaces
- C25D5/56—Electroplating of non-metallic surfaces of plastics
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
- C25D7/0621—In horizontal cells
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/24—Reinforcing the conductive pattern
- H05K3/241—Reinforcing the conductive pattern characterised by the electroplating method; means therefor, e.g. baths or apparatus
Definitions
- the invention relates to a device for electroplating at least one electrically conductive substrate or an electrically conductive structure on a non-conductive substrate, which comprises at least one bath, an anode and a cathode, wherein the bath contains an electrolyte solution containing at least one metal salt, from the metal ions be deposited on electrically conductive surfaces of the substrate to form a metal layer.
- the invention further relates to a process for the galvanic coating of at least one substrate, which is carried out in a device designed according to the invention.
- Galvanic coating methods are used, for example, to coat electrically conductive substrates or structured or full-area electrically conductive surfaces on non-conductive substrates. With these methods, it is possible, for example, to produce conductor tracks on printed circuit boards, RFID antennas, flat cables, thin metal foils, conductor tracks on solar cells, and to galvanically coat other products, such as two- or three-dimensional objects, for example plastic molded parts.
- DE-B 103 42 512 discloses an apparatus and a method for the electrolytic treatment of electrically mutually insulated, electrically conductive structures on surfaces of band-shaped material to be treated.
- the material to be treated is conveyed continuously on a transport path and in a transport direction, wherein the material to be treated is contacted with a contacting electrode arranged outside of an electrolysis region, whereby negative voltages are applied to the electrically conductive structures.
- a contacting electrode arranged outside of an electrolysis region, whereby negative voltages are applied to the electrically conductive structures.
- metal ions are deposited on the electrically conductive structures from the treatment liquid to form a metal layer.
- An electroplating apparatus in which the contacting unit is arranged in the electrolyte bath is disclosed, for example, in DE-A 102 34 705.
- the galvanization device described here is suitable for coating structures that are already conductive and that are arranged on a band-shaped carrier.
- the contacting takes place in this case via rollers which are in contact with the conductive structures. Since the rollers are in the electrolyte bath, metal also separates out from the electrolyte bath.
- the rollers are made up of individual segments which are switched cathodically, as long as they are in contact with the structures to be coated and are switched anodically, if there is no contact of roller and electrically conductive structure.
- the object of the invention is to provide a device which ensures a sufficiently long contact time even for short structures, so that even short structures can be provided with a sufficiently thick metal layer.
- a device for electroplating at least one electrically conductive substrate or a structured or full-surface electrically conductive surface on a non-conductive substrate which comprises at least one bath, an anode and a cathode, wherein the bath is at least one metal salt contains containing electrolyte solution. From the electrolytic solution, metal ions are deposited on electrically conductive surfaces of the substrate to form a metal layer.
- the at least one cathode is brought into contact with the surface of the substrate to be coated, while the substrate is conveyed through the bath.
- the at least one cathode comprises at least one band with at least one electrically conductive section, which is guided around at least two rotatable shafts.
- the waves are carried out with a suitable, matched to the respective substrate cross-section.
- the waves are cylindrically shaped and may for example be provided with grooves in which the at least one band runs.
- the shaft is designed such that the current is transmitted from the surface of the shaft to the band.
- the shafts are provided with grooves in which the at least one belt runs, the substrate can be contacted simultaneously via the shafts and the belt.
- the grooves can be electrically conductive and the regions of the waves between the grooves can be made of an insulating material in order to avoid that the substrate is also electrically contacted via the waves.
- the shaft is supplied with power via slip rings, for example, but it is also possible to use any other suitable device with which current can be transmitted to rotating shafts.
- the cathode comprises at least one band with at least one electrically conductive portion, even substrates with short electrically conductive structures, especially in the transport direction of the substrate, can be provided with a sufficiently thick coating. This is possible since, according to the invention, by the design of the cathode as a band, even short electrically conductive structures are in contact with the cathode for a longer time than is the case with the methods known from the prior art.
- At least two bands are arranged offset one behind the other.
- the arrangement is preferably such that the second band arranged behind the first band contacts the electrically conductive structure in the region on which the metal was deposited during the contacting with the first band.
- more than two bands are connected in series.
- each successive, offset bands arranged over at least one common shaft.
- the rear shaft of the first belt is at the same time the front shaft of the second belt.
- waves can be saved and the bath can be kept shorter.
- each successive, staggered bands are guided over at least one common shaft, it is also possible to guide the successively arranged bands via respective independent waves. In such an arrangement, it is advantageous if the waves are designed so that they can be lifted from the substrate nen.
- metal is also deposited on the bands and the waves.
- bands are each arranged independently on waves, individual bands together with their waves can each be lifted from the substrate and anodically switched, while at the same time bands arranged upstream or downstream of the raised bands guide the substrate and the electrically conductive structures located thereon.
- the metal deposited on the bands and shafts can only be released while removing production interruptions.
- the at least one band has a network structure.
- the advantage of the network structure is that in each case only small areas of the electrically conductive structures to be coated on the substrate are covered by the band. The coating takes place in the holes of the net.
- the bands are designed in the form of a network structure to arrange at least two bands one behind the other. It is also possible to connect two bands formed as nets directly one behind the other, the nets then each having different mesh sizes and / or different mesh shapes to coat also the areas in which the front net rests.
- webs are to be understood as meaning tapes with individual holes formed therein.
- a formed in the form of a network band is that the network can extend over the entire width of the waves. It is not necessary to arrange several narrow bands formed in the form of nets next to each other.
- the width of the tapes depends on the production options. The narrower the bands can be formed, the smaller the conductive structures can be coated.
- An advantage of narrow bands with small distances from one another is that the contact probability of the smallest structures is thereby greater than with a smaller number of broad bands. Since the contact surface of the bands by covering the structures just below the band inhibits the deposition, it is advantageous to minimize this coverage effect by narrow bands.
- the electrolyte purging of the surfaces to be metallized becomes more uniform by a multiplicity of smaller surface accesses than in the case of a few surface accesses, such as are present in a small number of wide bands.
- the number of juxtaposed bands depends on the width of the substrate. The wider the substrate to be coated, the more ribbons must be placed side by side. In this case, care must be taken that a free gap remains between the bands, in which the metal can be deposited on the electrically conductive substrate or the structured or full-surface electrically conductive surface of the substrate. If at least two bands are arranged offset one behind the other, the gap between two juxtaposed bands is preferably as wide as the band arranged behind it.
- the at least one band comprises alternately conductive and non-conductive sections.
- the portions of the tape which contact the substrate to be coated are switched cathodically and the portions of the tape which are not in contact with the substrate become anodic.
- the advantage of this circuit is that metal which deposits on the tape during the cathodic circuit of the tape is removed during the anodic circuit.
- the anodized region is preferably longer or at least as long as the cathodically connected region.
- this can be achieved in that the anodically connected wave has a larger diameter than the cathodically connected waves, on the other hand, it is also possible to provide at least the same or smaller diameter of the anodically connected waves, at least as many as cathodically connected waves, wherein the Distance of the cathodically connected waves and the distance of the anodically connected waves is preferably the same size.
- the length of the conductive sections is preferably greater than or equal to the distance between two adjacent cathodically connected waves.
- a coating on the electrically conductive structure of the substrate then takes place from the first contact of the electrically conductive structure the cathodically connected portion of the tape to the time at which the contact of the cathodically connected portion of the tape is terminated with the electrically conductive structure on the substrate.
- band bands with alternating conductive and non-conductive sections for example, link bands can be used, in which the individual members are fastened to each other, for example by means of clamps. According to the required length of the conductive portions, a corresponding number of electrically conductive members are mounted one behind the other. In order to produce a non-electrically conductive portion, at least one non-conductive member is inserted between two electrically conductive members. In addition to the structure as a link chain, it is also possible to provide at least one electrically non-conductive, flexible band as a carrier, which at predetermined intervals against each other electrically insulated mounted electrically conductive sections.
- a conductive material are here, for example, wire or films, with which the carrier is wrapped or flexible or rigid films, which may for example be in the form of a network or holes may have, which are connected to the carrier.
- the connection with the carrier can be done for example by gluing.
- a plurality of carriers may be arranged side by side, which are interconnected by common conductive portions. Between the individual carriers, a gap is preferably formed in this case.
- the carriers contain holes or have a reticulated structure.
- the electrically conductive reticulated sections can be formed, for example, by means of a wire, which is guided through the individual meshes of the network structure, are connected to the meshes of a non-conductive section.
- the band can also have any further structure by means of which conductive and non-conductive sections can be realized alternately.
- the device for electroplating further comprises a device with which the substrate can be rotated.
- the axis of rotation of the device, with which the substrate can be rotated is arranged perpendicular to the surface of the substrate to be coated, if by turning electrically conductive structures, which are initially seen in the transport direction of the substrate, wide and short, so to be aligned that after the Drew hen seen in the transport direction are narrow and long. By turning different coating times are compensated, which result from the fact that a coating takes place already with the first contact of the electrically conductive structure with the cathodically connected band.
- the substrate When coated on multiple sides of the substrate, it can preferably be rotated in the device with which the substrate can be rotated so that, after rotation, the surface to be coated next points in the direction of the cathode.
- At least two bands are arranged such that the substrate to be coated is passed between them and the bands contact the upper side and the lower side of the substrate, respectively.
- the structure of the device for galvanic coating is preferably such that the transport plane of the substrate acts as a mirror plane.
- films are to be coated whose length exceeds the length of the bath - so-called continuous films, which are initially unwound from a roll, passed through the device for electroplating and then wound up again - these can, for example, also zig-zag or in shape a meander around one or more galvanic coating devices according to the invention, which can then be arranged, for example, one above the other or next to one another, through the bath.
- the devices can each be aligned at any angle in the bath.
- the electroplating devices are arranged one above the other, it is also possible to simultaneously coat the films on the upper side and the lower side by passing them between two devices which contact the film at their top and bottom side and after passing through is deflected by one of the devices, to then be passed between this and another device disposed above or below the device.
- the coating takes place in that the metal layers deposited on the upper side and the underside deposited on the lower side grow together in the hole.
- a conductive hole wall is provided, which is coated by the method according to the invention. As a result, then also the entire wall of the hole can be coated. If not the entire perforated wall is electri- is conductive, the coating of the entire hole wall takes place here by growing together of the metal layers.
- the shafts are both anodically and cathodically switchable in a preferred embodiment and can be lowered onto the substrate or lifted from the substrate become. While the waves are raised from the substrate and are not in contact with the substrate, they can be anodically switched. While the waves are connected anodically, the metal deposited thereon is removed again. At the same time, the at least one band circulating the waves is connected anodically, so that the metal deposited thereon is also removed therefrom. The waves, which are in contact with the substrate via the at least one strip, are connected cathodically.
- the waves may also contain a plurality of electrically conductive regions, of which at least one is connected anodically and at least one further cathodically.
- the circulating band in the cathodically connected region of the shaft, the circulating band is also switched cathodically, so that a coating of the electrically conductive substrate or the structured or full-surface electrically conductive surfaces of the substrate takes place while in the anodic region, the previously undesired deposited metal of the Wave and / or the at least one band is removed again.
- the band it is necessary for the band to have electrically isolated sections which are arranged on the shafts so that an electrically conductive area of the band does not simultaneously touch an anodically connected area and a cathodically connected area on the shaft in order to avoid a short circuit ,
- the electrically conductive sections of the at least one band as well as the wave surfaces or the wavebands which are in contact with the at least one band are preferably made of an electrically conductive material which does not change into the electrolytic solution during operation of the device.
- Suitable materials for the fabrication of the conductive portions of the tape and the wave surfaces or regions which are in contact with the at least one tape are, for example, metals, graphite, conductive polymers such as polythiophenes or metal / plastic composites.
- Preferred materials are stainless steel and / or titanium.
- anodes can serve, with different polarity of the waves, the anodically connected waves, on the other hand, it is also possible to additionally provide anodes in the bath.
- the anodes are preferably arranged as close as possible to the structure to be coated.
- the anodes may each be arranged between two cathodically connected waves.
- Suitable material for the anodes is on the one hand any material known to those skilled in the art for insoluble anodes. Preference is given here, for example, stainless steel, graphite, platinum, titanium or metal / plastic composites.
- detachable anodes These then preferably contain the metal, which is deposited galvanically on the electrically conductive structures.
- the anodes can take any known form to those skilled in the art.
- flat rods can be used as anodes, which have a minimum distance to the substrate surface during operation of the device, and which can be pulled out of the device in a position change of the waves in the direction of the shaft axes. It is also possible to use flat sheets as anodes, which can be folded upwards or downwards by 90 ° between the roll lifting paths. Another possibility is to provide elastic wires, preferably spiral wires, as anodes, which can be pulled upwards or downwards from the device or introduced into it from winding / unwinding devices.
- the galvanic coating device can be used for any conventional metal coating.
- the composition of the electrolyte solution used for the coating depends on which metal the electrically conductive structures are to be coated on the substrate.
- Typical metals which are deposited by electroplating on electrically conductive surfaces are, for example, gold, nickel, palladium, platinum, silver, tin, copper or chromium.
- Suitable electrolyte solutions which can be used for the electroplating of electrically conductive structures are known to those skilled in the art, for example, from Werner Jillek, Gustl Keller, Handbuch der Porterplattentechnik, Eugen G. Leuze Verlag, 2003, Vol. 4, pages 332 to 352.
- the substrate For galvanic coating of the electrically conductive structures on the substrate, this is first supplied to the bath with the electrolyte solution.
- the substrate is then conveyed through the bath with the at least one ribbon of the cathode resting on the substrate to contact the electrically conductive structures, preferably with the belt moving at a rotational speed equal to the rate at which the substrate passes through the bath to be led.
- the transport of the sub strates through the bath can be done, for example, with a transport device, as known to those skilled in the art.
- it is also possible to arrange the device for coating so that the substrate rests on the at least one cathodically connected strip and is transported by the movement of the strip through the bath.
- the transport of the substrate through the bath, in which the at least one band of the device for coating acts as a transport device, is particularly advantageous if the substrate is to be coated on the upper side and on the lower side.
- the substrate rests on one device while it is pressed by the other device to the device on which it rests.
- the movement of the belts then transports the substrate through the device.
- At least one further transport roller which preferably consists of an electrically insulating material, can transport the substrate through the bath.
- a combination of at least one band with at least one additional transport roller is also possible.
- the number of required transport rollers depends on the size of the substrate to be coated. The distance of the transport rollers must be selected so that always at least one transport roller with the substrate in contact, unless the transport is done by the bands.
- the transport can also be realized by the winding and unwinding unit, which is preferably arranged outside the bath.
- the transport of the substrate takes place through the shafts and / or through the belt when they are driven.
- one-sided coating is preferably at least one pressure roller or a pressing belt is provided, with which the substrate is pressed against the cathodically connected areas.
- Good contact between the cathodically connected tape and the substrate to be coated can also be achieved by pressing the tape against the substrate via the weight of the corrugations that surround it. It is also possible to generate an additional contact pressure in that the band is pressed against the substrate via a resilient mounting of the shafts.
- the drive of the waves is preferably outside the bath. In a preferred embodiment, all waves are driven. However, it is also possible to drive only individual waves. When a transport device independent of the cathodes is provided, the belts can be driven by the substrate in contact with them, with no shaft circulating around the belt being provided with its own drive. However, it is also possible to drive the band in addition by at least one wave that revolves around it.
- the shafts are driven by a common drive unit.
- the drive unit is preferably an electric motor.
- the shafts are preferably connected to the drive via a chain or belt transmission. But it is also possible to provide each of the shafts with gears that mesh with each other and over which the waves are driven. In addition to the possibilities described here, any other suitable drive known to those skilled in the art for driving the shafts can also be used.
- the at least one band is supplied with voltage via the waves that surround it.
- the waves can be electrically conductive over the entire surface or partially at the surface.
- contact means may, for example, be brushes which are in contact with the electrically conductive portions of the tape.
- the power will be supplied via the waves.
- the power supply of the waves takes place preferably outside of the bath. Suitable means for transmitting current to the shafts are, for example, slip rings arranged on the shafts.
- the cathodically switched waves are raised from the substrate for demetallation, while at the same time the anodically connected waves are lowered onto the substrate. Simultaneously with the wave change, the previously cathodically switched waves are switched anodically so that the metal deposited thereon is removed, and the previously anodically connected waves are switched cathodically so that the electrically conductive structures on the substrate can be further coated.
- Such a wave change is preferably carried out while the cathodically connected strip section just does not contact a structure to be coated.
- at least one preferably insulated shaft as tensioning roller, so that all waves are switched cathodically to change the shaft, then the previously anodically switched waves are lowered onto the substrate, the previously cathodically switched waves are lifted from the substrate and, after these were raised to be anodically switched.
- the device is disposed below the substrate, the previously cathodically switched waves are lowered and then anodized, while the previously anodically switched waves are raised against the substrate and then switched to cathodic.
- insulated transport shafts or tension shafts are provided, the lowering and raising of the shafts as well as the polarity reversal can take place simultaneously.
- shields on the cathodically connected waves which reduce metal deposition on the waves.
- Such shields are, for example, nonconductive sheaths of the shafts which cover the shafts in the areas in which they are in contact with the electrolyte solution, the sheaths being at a very small distance from the shaft surface and releasing the shafts only at the points where the shroud is located Substrate and / or the bands are contacted.
- the substrate to be coated is rotated after passing through the device for galvanic coating by a predetermined angle. After rotation, the substrate either passes through the device a second time or a second corresponding device.
- the angle through which the substrate is rotated is preferably in the range of 10 ° to 170 °, more preferably in the range of 50 ° to 140 °, in particular in the range of 80 ° to 100 °, and most preferably the angle is the substrate is rotated, substantially 90 °.
- 90 ° means that the angle through which the substrate is rotated does not deviate more than 5 ° from 90 °.
- the device for rotating the substrate can be arranged inside or outside the bath.
- the axis of rotation is perpendicular to the surface to be coated.
- the rotation axis is arranged so that after rotation, the substrate is positioned so that the surface to be coated next faces the cathode.
- the layer thickness of the metal layer deposited on the electrically conductive structure by the method according to the invention depends on the contact time, which results from the passage speed of the substrate through the device and the number of bands positioned behind one another, and the current intensity with which the device is operated.
- a higher contact time can be achieved, for example, by connecting several devices according to the invention in series in at least one bath.
- a plurality of devices according to the invention are connected in series in each case in individual baths. This makes it possible to hold in each bath a different electrolyte solution to sequentially deposit different metals on the electrically conductive structures. This is advantageous, for example, in decorative applications or in the production of gold contacts.
- the respective layer thicknesses are adjustable by the choice of the flow rate and the number of devices with the same electrolyte solution.
- all electrically conductive surfaces can be coated, regardless of whether electrically insulated structures insulated from one another are to be coated on a nonconductive substrate or a full surface area.
- the device is preferably used for coating electrically conductive structures on a non-electrically conductive support, for example reinforced or unreinforced polymers, such as are conventionally used for printed circuit boards, ceramic materials, silicon, glass, textiles, etc.
- the thus produced, galvanic Coated electrically conductive structures are, for example, conductor tracks.
- the electrically conductive structures to be coated can be printed on the printed circuit board, for example, from an electrically conductive material.
- the electrically conductive structure preferably contains either particles of any geometry made of an electrically conductive material in a non-conductive matrix or consists essentially of the electrically conductive material.
- Suitable electrically conductive materials are, for example, carbon or graphite, metals, preferably aluminum, iron, gold, copper, nickel, silver and / or alloys or metal mixtures containing at least one of these metals, electrically conductive metal complexes, conductive organic compounds or conductive polymers.
- a pretreatment is first required to make the structures electrically conductive. This may be, for example, a chemical or a mechanical pretreatment such as a suitable cleaning. As a result, for example, the oxide layer of metals which is troublesome for the electroplating is removed.
- the electrically conductive structures to be coated can also be applied to the printed circuit boards by any other methods known to those skilled in the art.
- Such printed circuit boards are installed, for example, in products such as computers, telephones, televisions, electrical automotive components, keyboards, radios, video, CD, CD-ROM and DVD players, game consoles, measuring and control devices, sensors, electrical kitchen appliances, electric Toys etc.
- electrically conductive structures can be coated on flexible circuit carriers.
- flexible circuit carriers are, for example, polymer films, such as polyimide films, PET films or polyolefin films, on which electrically conductive structures are printed.
- the device according to the invention and the method according to the invention are suitable for the production of RFID antennas, transponder antennas or other antenna structures, chip card modules, flat cables, seat heaters, foil conductors, printed conductors in solar cells or in LCD or plasma picture screens, thin metal foils or for the production of electroplated products in any desired form, such as, for example, single-sided or double-sided metal-clad polymer supports with defined layer thickness, 3D-molded interconnect devices or also for the production of decorative or functional surfaces on products, for example for shielding from electromagnetic radiation, for heat conduction or as packaging become.
- the production of contact points or contact pads or wiring on an integrated electronic component is possible.
- the substrate After leaving the device for galvanic coating, the substrate can be further processed according to all steps known to those skilled in the art. For example, existing electrolyte residues can be removed from the substrate by rinsing and / or the substrate can be dried.
- the device according to the invention for the electroplating of electrically conductive substrates or of electrically conductive structures on electrically non-conductive substrates can be equipped with any additional device known to the person skilled in the art as required.
- ancillary devices include, for example, pumps, filters, chemical feeders, roll-up and roll-down devices, etc.
- the advantage of the device according to the invention and of the method according to the invention is that the at least one strip provides a larger contact surface and thus a longer contact time than is the case with the exclusive use of rollers known from the prior art , As a result, the desired layer thicknesses of electrically conductive structures within a shorter distance can be achieved, whereby the plants can be built shorter or can be operated at a higher throughput, whereby lower operating costs are achieved.
- Another significant advantage is that now even very short structures, as they are desired for example in the production of printed circuit boards, faster, more targeted and above all reproducible and can be realized with homogeneous layer thicknesses than with the roll systems known from the prior art is possible.
- FIG. 1 shows a plan view of an inventively designed device with a plurality of successively staggered bands
- FIG. 2 shows a side view of the device according to FIG. 1,
- FIG. 3 shows a side view of a device according to the invention with bands resting on the shaft
- FIG. 4 shows a top view of the device according to FIG. 3,
- FIG. 5 shows a side view of a device according to the invention with bands which lie in grooves of the shaft
- FIG. 6 shows a plan view of a device according to FIG. 5
- FIG. 7 shows a side view of a device designed according to the invention with cathodically and anodically connected shafts
- FIG. 8 shows a detail of a band, as used for example in FIG. 7,
- FIG. 9 shows a detail of an inventively designed device in which the anodically and the cathodically switched waves can be raised or lowered
- FIG. 10 shows a device according to the invention in which the top and bottom sides of a substrate are coated
- FIG. 11 shows a device with which top and bottom sides of a substrate can be coated, in which bands arranged one behind the other are arranged,
- FIG. 12 is an enlarged view of a section of a band in a first embodiment
- FIG. 14 shows a plan view of a detail of a band in a third embodiment
- FIG. 15 shows a side view of the band according to FIG. 14,
- Figure 16 is a side view of a device according to the invention with segmented
- FIG. 17 shows a side view of anodes during the galvanic coating
- Figure 18 is a side view of the anodes according to Figure 17 when changing the waves.
- Figure 1 shows a plan view of a cathode formed according to the invention, in which a plurality of bands are arranged offset one behind the other.
- a cathode 1 comprises a plurality of bands 2, which are each guided over two shafts 3.
- Adjacent bands 2 are arranged so that a gap 4 is formed between them.
- the width of the gap 4 is preferably greater than or equal to the width of a belt 2.
- one shaft 3 simultaneously serves as the rear shaft of the bands 2 of a first row and as the front shaft 3 for the bands 2 of a second row.
- the coating in the embodiment shown in FIG. 1 takes place in each case in the gaps 4 between the bands 2, as long as the electrically conductive structures which are to be coated are touched by a band 2.
- FIG. 2 shows a side view of the arrangement from FIG. 1.
- the bands 2 are each guided by two shafts 3.
- the waves are arranged in series one behind the other.
- the substrate to be coated may be in contact with the cathode 1 either at the top 5 or at the bottom 6. In this case, it is only necessary to ensure that the electrically conductive structures to be coated are assigned to the strip 2.
- the cathode 1 can simultaneously serve as a transport device.
- a device is additionally provided with which the substrate is placed against the bands 2 in order to produce an electrical contact of the underside 6 of the cathode 1 with the substrate to be coated.
- This device is preferably a transport device.
- Such devices are, for example, conveyor belts or transport shafts.
- each shaft 3 which is circulated by a band 2 is connected cathodically. Furthermore, it is also possible to switch each shaft 3 cathodically.
- anodes 31 In order to enable a galvanic coating, anodes 31 must be provided in the bath in addition to the cathode 1.
- the anodes 31 can either be arranged as shown in Figure 2 between the waves 3 or above or below the belt 2.
- FIG. 5 shows a side view and in FIG. 6 a plan view of an embodiment in which the bands 2 are received in grooves 30 in the shafts 3.
- the width of a groove 30 preferably corresponds to the width of a band 2 and the depth of a groove 30 preferably the thickness of a band 2.
- FIG. 7 shows a further embodiment of a device according to the invention for galvanic coating in a sectional representation.
- the device comprises a band 2, which is guided around a plurality of shafts 3.
- the shafts 3 are arranged in an upper row 9 and a lower row 10.
- the waves of the lower row 10 are connected cathodically, while the waves of the upper row 9 are connected anodically.
- Via the band 2 the voltage of the cathodically connected waves of the lower row 10 is transmitted to the electrically conductive structure 7.
- the electrically conductive structure 7 is also charged negatively, so that metal ions from the electrolyte solution in which the substrate
- anodes 31 may be arranged between the cathodes, as shown here.
- the anodes 31 are formed, for example, as flat bars.
- the band 2 in the embodiment shown in FIG. 7 is constructed as shown in FIG.
- the band 2 comprises electrically conductive sections 12 and electrically non-conductive sections, ie insulating sections 13.
- the length L of an electrically conductive section 12 is preferably greater than or equal to the distance h of two cathodically connected channels 3.
- the length L of an electrically conductive may be smaller than the distance d of a cathodically connected wave to an adjacent anodically connected wave.
- the transport direction of the substrate 8 is shown.
- 8 pressing rollers 21 are arranged below the substrate.
- the substrate 8 is passed between the pressure rollers 21 and the belt 2.
- the required contact pressure can be achieved on the one hand, that the pressure rollers 21 are fixedly mounted and the shafts 3, which surrounds the belt 2, are resiliently mounted and pressed against the substrate 8 or the shafts 3 are fixedly mounted and the pressure rollers 21 are movable stored and are moved against the substrate 8 with the required contact force.
- the pressure rollers 21 are fixedly mounted and the required contact pressure by the movable shafts 3 of the lower row 10 on the submersible strat 8 is applied.
- a further apparatus for galvanic coating may also be arranged below the substrate 8. In this case, the substrate 8 can then be simultaneously coated on its top and bottom.
- FIG. 9 shows a side view of a device designed according to the invention in a further embodiment.
- the waves of the anodized upper row 9 are offset from the waves of the cathodically connected lower row 10 is arranged.
- the distance h between two anodically connected waves or between two cathodically connected waves is chosen so that in each case an anodically connected wave can be passed between two adjacent cathodically switched waves and a cathodically connected wave between adjacent anodically connected waves.
- the arrows 15 is shown in Figure 9 that the waves of the lower row 10 can be raised and the waves of the upper row 9 can be lowered. This makes it possible to remove the metal deposited on the cathodically connected waves even during ongoing production operation.
- the cathodically connected waves of the lower row 10, as shown by the arrows 15, raised while the waves of the upper row 9, as shown by the arrows 16, are lowered.
- the polarity of the waves is reversed, so that after lowering the upper row 9, these waves are switched cathodically and after raising the lower row 10, these waves are connected anodically.
- metal now deposits on the previously anodically connected waves of the upper row 9, which now form the lower row 10 and are connected cathodically, while the metal previously deposited on the cathodically connected waves of the lower row 10 is removed long these form the upper row 9 and are connected anodically.
- each row 9 at least one transport shaft, which is not electrically conductive.
- the transport shafts are preferably in each case the first and / or the last wave of a row 9, 10.
- the number of anodically connected waves is greater than that of the cathodically connected waves.
- the first shaft of the upper row 9 can always remain anodically connected and remain in place.
- FIG. 10 shows a device for galvanic coating in a further embodiment.
- the substrate 8 is simultaneously coated on the top and bottom.
- the substrate 8 is passed between an upper device 17 and a lower device 18.
- the distance between the upper device 17 and the lower device 18 is selected such that it corresponds exactly to the thickness of the substrate 8.
- the shafts 19 facing the substrate are in each case connected cathodically, while the shafts 20 facing away from the substrate are connected anodically.
- the polarity of the waves is reversed, so that the waves 20, as soon as they contact the substrate 8, are switched cathodically and the waves 19, as soon as they are lifted from the substrate 8, are connected anodically.
- several bands 2 are arranged one behind the other at the top side and at the bottom side of the substrate 8 arranged.
- the bands 2 are each guided by separate waves.
- the belts 2 arranged one behind the other are arranged offset relative to one another.
- FIG. 11 corresponds largely to the embodiment shown in FIG.
- a cathodically connected shaft 19 and an anodically connected shaft 20 form the rear shaft of a belt 2 and at the same time the front shaft of another belt 22, which is shown here by dashed lines.
- the arrangement of the bands 2 and the further bands 22 shown in dashed lines corresponds to the arrangement shown in FIG.
- each of the bands 22 are arranged offset behind the bands 2.
- FIG. 12 shows an enlarged view of a first embodiment of a band according to the invention with electrically conductive and electrically non-conductive sections.
- the band 2 shown schematically here is composed of individual conductive segments 23 and non-conductive segments 24.
- the individual segments 23, 24 are each secured with brackets 25 to each other.
- the length of the conductive portions is determined by the number of conductive segments 23 attached to each other. Between two conductive sections, an electrically non-conductive portion is arranged in each case. In general, it is already sufficient to use a single electrically non-conductive segment 24 for the electrically non-conductive portion. However, it is also possible to arrange a plurality of non-conductive segments 24 one behind the other.
- FIG. 13 shows a further embodiment of a band 2.
- the band 2 is made of a flexible carrier 26 which is wrapped by an electrically conductive wire 27 to produce an electrically conductive portion 12.
- a flexible carrier 26 is suitable, for example, a non-conductive plastic tape, which is optionally made of an elastomer.
- the flexible carrier 26 may, for example, also be wound with an electrically conductive foil in order to produce the electrically conductive sections 12.
- a further embodiment of a band 2 is shown schematically in plan view in FIG. 14 and side view in FIG.
- the band 2 shown here comprises two flexible non-conductive supports 26, on which conductive portions 32 are fixed at regular intervals.
- the attachment of the conductive portions 32 on the non-conductive supports 26 can be done for example by gluing.
- the conductive portions 32 may be either rigid or flexible. In the case of rigid conductive sections 32, their width is preferably selected such that they can rotate around the corrugations 3. For this purpose, it is necessary that the width of the conductive portions 32 is smaller as the radius of the shaft 3. If the conductive portions 32 are to be made wider, they are preferably made of a flexible material. A suitable material is for example a still flexible metal foil.
- the non-conductive support 26 and / or the conductive portions 32 of the tape 2 may also be provided with holes or be made net-shaped.
- any other known in the art structure is possible from which a band can be produced, which alternately electrically conductive and electrically has non-conductive portions.
- a network structure as band 2, wherein an electrically conductive network is connected to an electrically non-conductive network, wire or polymer carrier in order to form the electrically conductive sections 12 and electrically non-conductive sections 13.
- the electrically conductive net-shaped sections can then be connected, for example with the aid of a wire, which is guided through the individual meshes of the network structure, to the meshes of a non-conductive section.
- FIG. 16 shows an embodiment of a device designed according to the invention, in which the shafts 3 are constructed from individual conductive segments 35 and non-conductive segments 36.
- the conductive segments 35 and the non-conductive segments 36 are alternately arranged. This makes it possible to anodically connect a conductive segment 35 cathodically and an adjacent conductive segment 35, which is separated by a non-conductive segment 36 from the cathodically connected segment 35.
- the band 2 revolving around the shafts 3 be embodied in individual conductive 12 and electrically non-conductive sections 13.
- the non-conductive portions 13 of the band 2 must be arranged so that they each rest against a non-conductive segment 36 of the shaft.
- Removal of the metal deposited on the cathodically connected segment 35 of the shaft and the cathodically connected section 12 of the strip 2 is achieved by switching them anodically in the further circulation.
- 3 sliding contacts 37, 38 are preferably provided on the shafts.
- the first sliding contact 37 serves as the anode
- the second sliding contact 38 as the cathode.
- FIG. 17 shows a side view of anodes during the galvanic coating.
- Figure 18 shows the anodes in a position when the shafts 3, which are not shown here, change position.
- shafts 3 or electrically conductive segments of the shafts 3 anodes 31 can be constructed, for example, as shown in Figures 17 and 18.
- the anodes 31 are in their extended position. In this case, they are arranged above and below the substrate 8 in the case of a substrate 8 which is simultaneously coated on the upper side and on the lower side.
- the anode 31 is preferably disposed on the side of the substrate 8 which is coated. Care must be taken here that the anode 31 does not touch the substrate. Otherwise, it could lead to a short circuit on the one hand, if the cathode touches the same electrically conductive structure as the anode, on the other hand would be removed during contact with the anode 31, the metal previously deposited on the structure again.
- the anodes 31, as shown in FIG. 18 by the double arrow 41, are movable parallel to the surface of the substrate 8 to be coated. The movement is transverse to the direction in which the substrate is transported through the bath. This makes it possible to remove the anodes while the shafts 3 change position. Damage to anodes 31 and 3 waves is thereby avoided.
- the anodes 31 are made of a flexible material. As a result, it is possible to wind up or unwind the anodes in respectively assigned anode winding / unwinding devices 40.
- the anode winder / unwind devices 40 are preferably located above and below the bath as shown here.
- Such anable and unwindable anodes are made for example in the form of flexible metal bands or elastic spirals. If the anodes are made of elastic spirals, preferably several of the spirals are fastened next to one another. LIST OF REFERENCE NUMBERS
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Abstract
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP07728172A EP2010699A2 (fr) | 2006-04-18 | 2007-04-17 | Dispositif et procédé de revêtement galvanique |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP06112723 | 2006-04-18 | ||
EP07728172A EP2010699A2 (fr) | 2006-04-18 | 2007-04-17 | Dispositif et procédé de revêtement galvanique |
PCT/EP2007/053707 WO2007118875A2 (fr) | 2006-04-18 | 2007-04-17 | Dispositif et procédé de revêtement galvanique |
Publications (1)
Publication Number | Publication Date |
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EP2010699A2 true EP2010699A2 (fr) | 2009-01-07 |
Family
ID=38236519
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP07728172A Withdrawn EP2010699A2 (fr) | 2006-04-18 | 2007-04-17 | Dispositif et procédé de revêtement galvanique |
Country Status (11)
Country | Link |
---|---|
US (1) | US20090101511A1 (fr) |
EP (1) | EP2010699A2 (fr) |
JP (1) | JP2009534527A (fr) |
KR (1) | KR20090009876A (fr) |
CN (1) | CN101473072A (fr) |
BR (1) | BRPI0710241A2 (fr) |
CA (1) | CA2649786A1 (fr) |
IL (1) | IL194754A0 (fr) |
RU (1) | RU2420616C2 (fr) |
TW (1) | TW200811316A (fr) |
WO (1) | WO2007118875A2 (fr) |
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EP1919703B1 (fr) | 2005-08-12 | 2013-04-24 | Modumetal, LLC | Materiaux composites a composition modulee et leurs procedes de fabrication |
TW200829726A (en) * | 2006-11-28 | 2008-07-16 | Basf Ag | Method and device for electrolytic coating |
CN101970720B (zh) * | 2008-03-13 | 2014-10-15 | 巴斯夫欧洲公司 | 施加金属层至基质的方法和分散体及可金属化热塑性模塑组合物 |
NL1035265C2 (nl) * | 2008-04-07 | 2009-10-08 | Meco Equip Eng | Werkwijze en inrichting voor het elektrolytisch galvaniseren van niet-metallische glasachtige substraten. |
EA029168B1 (ru) | 2009-06-08 | 2018-02-28 | Модьюметал, Инк. | Электроосажденное наноламинатное покрытие и оболочка для защиты от коррозии |
TW201121680A (en) * | 2009-12-18 | 2011-07-01 | Metal Ind Res & Dev Ct | Electrochemical machining device and machining method and electrode unit thereof. |
KR101103450B1 (ko) * | 2010-07-27 | 2012-01-09 | 주식회사 케이씨텍 | 기판 도금 장치 |
US20120231574A1 (en) * | 2011-03-12 | 2012-09-13 | Jiaxiong Wang | Continuous Electroplating Apparatus with Assembled Modular Sections for Fabrications of Thin Film Solar Cells |
US10472727B2 (en) | 2013-03-15 | 2019-11-12 | Modumetal, Inc. | Method and apparatus for continuously applying nanolaminate metal coatings |
CA2905575C (fr) | 2013-03-15 | 2022-07-12 | Modumetal, Inc. | Procede et appareil d'application en continu de revetements metalliques nanostratifies |
CA2905513C (fr) | 2013-03-15 | 2022-05-03 | Modumetal, Inc. | Revetement nanostratifie de chrome et de nickel ayant une durete elevee |
WO2014146114A1 (fr) | 2013-03-15 | 2014-09-18 | Modumetal, Inc. | Revêtements nanostratifiés |
BR112015022192A8 (pt) | 2013-03-15 | 2019-11-26 | Modumetal Inc | artigo e seu método de preparação |
RU2534794C2 (ru) * | 2013-03-21 | 2014-12-10 | Открытое акционерное общество "Научно-исследовательский институт конструкционных материалов на основе графита "НИИграфит" | Способ связывания волокнистого пан материала при проведении стадий получения из него углеродного волокна |
EP2799939A1 (fr) * | 2013-04-30 | 2014-11-05 | Universo S.A. | Support pour le traitement de pièces de micromécanique |
KR101419276B1 (ko) * | 2013-08-27 | 2014-07-15 | (주)엠에스티테크놀로지 | 플라즈마 전해 산화에 의한 코팅 형성 방법 |
CN106795645B (zh) * | 2014-09-18 | 2020-03-27 | 莫杜美拓有限公司 | 用于连续施加纳米层压金属涂层的方法和装置 |
BR112017005534A2 (pt) | 2014-09-18 | 2017-12-05 | Modumetal Inc | métodos de preparação de artigos por processos de eletrodeposição e fabricação aditiva |
DE102015121349A1 (de) | 2015-12-08 | 2017-06-08 | Staku Anlagenbau Gmbh | Vorrichtung zur Oberflächenbehandlung eines Endlosmaterials sowie deren Verwendung |
KR101681083B1 (ko) * | 2016-06-26 | 2016-12-01 | 주식회사 지에스아이 | 곡면부를 포함하는 상대전극을 갖는 도금장치 |
WO2018049062A1 (fr) | 2016-09-08 | 2018-03-15 | Modumetal, Inc. | Procédés pour obtenir des revêtements stratifiés sur des pièces et articles fabriqués à partir de ceux-ci |
KR102412452B1 (ko) | 2016-09-14 | 2022-06-23 | 모두메탈, 인크. | 신뢰가능한 고처리량 복합 전기장 발생을 위한 시스템, 및 그로부터 코팅을 제조하는 방법 |
WO2018085591A1 (fr) | 2016-11-02 | 2018-05-11 | Modumetal, Inc. | Structures d'emballage à couches d'interface de haute densité de topologie optimisée |
US11293272B2 (en) | 2017-03-24 | 2022-04-05 | Modumetal, Inc. | Lift plungers with electrodeposited coatings, and systems and methods for producing the same |
CN110770372B (zh) | 2017-04-21 | 2022-10-11 | 莫杜美拓有限公司 | 具有电沉积涂层的管状制品及其生产系统和方法 |
WO2019210264A1 (fr) | 2018-04-27 | 2019-10-31 | Modumetal, Inc. | Appareils, systèmes et procédés de production d'une pluralité d'articles pourvus de revêtements nano-stratifiés à l'aide d'une rotation |
CN110952121B (zh) * | 2018-12-17 | 2023-12-05 | 嘉兴瑞通智能装备有限公司 | 焊带制造装置和电镀机构及其电镀方法 |
CN113512749A (zh) * | 2020-12-08 | 2021-10-19 | 郑州大学 | 一种电镀金刚石刀具实验装置 |
CN117136257A (zh) | 2021-04-21 | 2023-11-28 | 三菱电机株式会社 | 电镀电极和使用该电镀电极的电镀方法 |
CN113400698B (zh) * | 2021-05-11 | 2022-12-20 | 重庆金美新材料科技有限公司 | 一种导电传动带及其制备方法、薄膜水电镀设备 |
CN115896907A (zh) * | 2022-10-19 | 2023-04-04 | 重庆金美新材料科技有限公司 | 一种阴极导电机构和电镀系统 |
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DE1756267A1 (de) * | 1968-04-27 | 1971-10-07 | Carl Klingspor | Galvanisiervorrichtung fuer Gewebe |
LU80496A1 (fr) * | 1978-11-09 | 1980-06-05 | Cockerill | Procede et diopositif pour le depot electrolytique en continu et a haute densite de courant d'un metal de recouvrement sur une tole |
DE4413149A1 (de) * | 1994-04-15 | 1995-10-19 | Schmid Gmbh & Co Geb | Einrichtung zur Behandlung von Gegenständen, insbesondere Galvanisiereinrichtung für Leiterplatten |
WO2003038158A2 (fr) * | 2001-10-25 | 2003-05-08 | Infineon Technologies Ag | Dispositif de galvanisation et systeme de galvanisation concus pour revetir des structures deja conductrices |
DE10234705B4 (de) * | 2001-10-25 | 2008-01-17 | Infineon Technologies Ag | Galvanisiereinrichtung und Galvanisiersystem zum Beschichten von bereits leitfähig ausgebildeten Strukturen |
DE10342512B3 (de) * | 2003-09-12 | 2004-10-28 | Atotech Deutschland Gmbh | Vorrichtung und Verfahren zum elektrolytischen Behandeln von elektrisch gegeneinander isolierten, elektrisch leitfähigen Strukturen auf Oberflächen von bandförmigem Behandlungsgut |
-
2007
- 2007-04-17 CN CNA2007800226453A patent/CN101473072A/zh active Pending
- 2007-04-17 US US12/297,864 patent/US20090101511A1/en not_active Abandoned
- 2007-04-17 CA CA002649786A patent/CA2649786A1/fr not_active Abandoned
- 2007-04-17 JP JP2009505867A patent/JP2009534527A/ja not_active Withdrawn
- 2007-04-17 EP EP07728172A patent/EP2010699A2/fr not_active Withdrawn
- 2007-04-17 WO PCT/EP2007/053707 patent/WO2007118875A2/fr active Application Filing
- 2007-04-17 BR BRPI0710241-0A patent/BRPI0710241A2/pt not_active IP Right Cessation
- 2007-04-17 KR KR1020087028157A patent/KR20090009876A/ko not_active Application Discontinuation
- 2007-04-17 RU RU2008145108/02A patent/RU2420616C2/ru not_active IP Right Cessation
- 2007-04-18 TW TW096113679A patent/TW200811316A/zh unknown
-
2008
- 2008-10-22 IL IL194754A patent/IL194754A0/en unknown
Non-Patent Citations (1)
Title |
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See references of WO2007118875A2 * |
Also Published As
Publication number | Publication date |
---|---|
KR20090009876A (ko) | 2009-01-23 |
TW200811316A (en) | 2008-03-01 |
CN101473072A (zh) | 2009-07-01 |
WO2007118875A2 (fr) | 2007-10-25 |
CA2649786A1 (fr) | 2007-10-25 |
US20090101511A1 (en) | 2009-04-23 |
IL194754A0 (en) | 2009-08-03 |
RU2420616C2 (ru) | 2011-06-10 |
BRPI0710241A2 (pt) | 2011-08-09 |
JP2009534527A (ja) | 2009-09-24 |
RU2008145108A (ru) | 2010-05-27 |
WO2007118875A3 (fr) | 2008-08-07 |
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