WO2010133221A2 - Dispositif et procédé de mise en contact électrique d'un article dans des installations de galvanisation - Google Patents

Dispositif et procédé de mise en contact électrique d'un article dans des installations de galvanisation Download PDF

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Publication number
WO2010133221A2
WO2010133221A2 PCT/DE2010/000593 DE2010000593W WO2010133221A2 WO 2010133221 A2 WO2010133221 A2 WO 2010133221A2 DE 2010000593 W DE2010000593 W DE 2010000593W WO 2010133221 A2 WO2010133221 A2 WO 2010133221A2
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WO
WIPO (PCT)
Prior art keywords
electrolyte
contact
etching
wheels
contact means
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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.)
Ceased
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PCT/DE2010/000593
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German (de)
English (en)
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WO2010133221A3 (fr
Inventor
Egon Hübel
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Individual
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Publication of WO2010133221A2 publication Critical patent/WO2010133221A2/fr
Publication of WO2010133221A3 publication Critical patent/WO2010133221A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • C25D17/008—Current shielding devices
    • 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
    • C25D5/08—Electroplating with moving electrolyte e.g. jet electroplating
    • 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

Definitions

  • the invention relates to the electrical contacting of good, which is to be galvanized in continuous systems.
  • These are plate-shaped Good, z. B. of metal, plastic, ceramic, glass and other insulating materials which are electrically conductive at least on one side of the surface, such. B. printed circuit boards or conductor foils.
  • the invention is suitable for electroplating strip-shaped material from roll to roll.
  • the full-surface or structured electrically conductive surfaces of the material to be treated by the means of the invention must be cathodically connected to an anode for electroplating in an electrolyte.
  • the material is transported continuously or discontinuously by rotating or clinging means of transport. At the same time, these transport means act as the means of contact for the electrical contacting of the goods.
  • These contact materials are galvanized because of their cathodic polarity almost as well as the surface of the material. This metallization of the contact agent is very disturbing in continuous galvanizing. It must be continuously demetallised by the contact agents. For this purpose, proven solutions have already been proposed.
  • the object of the invention is to provide a device and a method that allow in continuous systems, the electrical contacting of the flat material to be galvanized by means of rotating, rigid or elastic contacts, said contacts should also be continuously demetallised without the production process having to be interrupted.
  • the contact means according to the invention consist of contact wheels or contact rollers which roll on the good to be electroplated.
  • the contact wheels are electrically conductive at least on the rolling circumference. Only a small portion of the rotating contact means is currently in the range of the electrolytic cell, d. H. in the area of the electric field that exists between the soluble or insoluble anode and the good to be plated as a cathode. The remaining area of the cathodic contact wheels is kept away from the electric field of the electrolytic cell by means of electrically non-conductive shields. Therefore, currently only the small part of a contact wheel is galvanized, which is close to the cathodic material and thus within the electrolytic cell. In the shielding area, the contact wheel is not metallised. There it is demetallised in electric-field-free space. According to the invention, this demetallization takes place without external current through chemical etching. As etchant, the electrolyte of the electrolytic cell or the
  • the electrolyte used has a redissolving, d. H. corrosive property, e.g. B. copper electrolyte based on sulfuric acid. This is used according to the invention for demetallizing the contact means.
  • the electrolyte is promoted during galvanization in the circuit to the good and through the working container.
  • a portion of the electrolyte stream is passed as a partial stream by means of an electrolyte conveying device to the surfaces to be demolded the contact means and there intense flows against this contact means outside the electrolytic cell of the electroplating process from close range.
  • the very small metallization which was deposited in the electrolytic cell with each revolution on the contact wheel, immediately redissolved.
  • the electrolyte which is flowed to the contact means, is enriched with at least one oxidizing agent, which are compatible with the respective electrolyte of the electroplating process, for.
  • oxidizing agent which are compatible with the respective electrolyte of the electroplating process, for.
  • oxygen As ozone, oxygen, atmospheric oxygen, hydrogen peroxide or peracids.
  • Chloride which is seeded as a salt in the flow of electrolyte flowing to the contact means, d. H. can be dosed.
  • the measures mentioned can be combined to increase the etching rate of the etching electrolyte, which flows against the contact wheels.
  • the measures for increasing the etching rate or for activating the electrolyte are particularly effective.
  • the chemical demetallization of the contact means also proves to be very advantageous in the use of elastic contact materials. These are described above Composite materials in the uncompressed state have a higher electrical resistance at the surface areas to be demetallised, which, however, has no influence on the demetallization according to the invention.
  • the undesired deposited on the contact metal metal is etched without power. Therefore, no residual metal surfaces or particles can form on the surface of the contact means, as can be done in the prior art.
  • the electrolyte When using insoluble anodes, the electrolyte must be continuously supplemented or regenerated with the respective metal ions of the deposition metal. This can be done by appropriate salts. For this purpose, a method which is described in the publication DD 215 589 Al is also suitable. A substance is added to the electrolyte as an electrochemically reversible redox system. This substance or the redox agent is conveyed with the electrolyte through the working container and a regeneration space in the circuit by means of at least one pump. It is oxidized at the insoluble anode and reduced again in the regeneration space under electroless dissolution of regeneration metal.
  • the deposition metal thereby dissolved is deposited in the electrolytic cell by means of plating current of a plating current source on the cathodic material.
  • a sulfuric acid electrolyte as used in printed circuit board technology, called.
  • the redox agent used is iron. Essentially, the following reactions take place in the working container and in the regeneration space:
  • the oxidized redox agent on the insoluble anode in this example iron, has the property of dissolving copper as ion Fe 3+ .
  • This is very advantageous in a further embodiment of the invention also for the electroless dissolution of the copper, which was deposited on the contact means used.
  • a particularly Fe 3+ -containing partial flow of the electrolyte conveyed in the circulation is branched off from the region of the anode and is intensively supplied to the contact means.
  • the copper Due to the intensive flow, the copper is dissolved much faster than the regeneration metal located in the regeneration space.
  • the regeneration metal to be dissolved is merely the flow of the recirculating exposed to th electrolyte. Impact of the liquid on the surface of the regeneration metal to increase the resolution is not given in the regeneration space in contrast to Entmetallmaschine the contact wheels according to the invention. For sufficient dissolution of metal therefore very many small pieces of metal are used in the regeneration space, which form a sufficiently large surface.
  • the inventive chemical demetallization of the contact wheels has the further advantage that the redissolved metal or its ions, is completely recycled to the metal-containing electrolyte. Thus, no loss of metal occurs. Moreover, it is a technically easy to implement process, which is therefore also very cost-effective.
  • electrically conductive materials or fillers can be used for the contact wheels, which are only chemically resistant and electrochemically unstable in the electrolyte. These materials, such as. As stainless steel, are considerably cheaper than the otherwise anodic resistant metals such. As titanium, niobium or tantalum. In a sulfuric acid copper electrolyte is stainless steel z. B. suitable with the trade name Hastelloy C. These materials can also be processed more economically than the above-mentioned electrochemically resistant metals. It is also advantageous that z.
  • FIG. 1 shows a contact wheel, which is partially flowed by a corrosive liquid for demetallization.
  • Figure 2 shows a continuous system in cross-section with a first embodiment of a galvanizing device according to the invention with soluble anodes.
  • FIG. 3 shows a continuous system in cross-section with a further embodiment of a galvanizing device according to the invention with soluble anodes.
  • FIG. 4 shows the embodiment of a continuous plating plant according to the invention with insoluble anodes and an electroless dissolution of the regeneration metal by means of a redox system.
  • FIG. 1 shows a rigid or elastic contact means as a contact wheel 2, which is located on a driven shaft 3. About this shaft 3, which is electrically insulated on its surface, the electric current for plating the contact wheel 2 is supplied. For this purpose serves z.
  • B a schematically illustrated sliding contact 15 or rotary contact on a shaft end.
  • the contact wheel 2 is electrically conductive on the running surface 4 over the entire circumference and is electrically connected to the sliding contact 15.
  • the end faces 5 of the contact wheels 2 are electrically insulated in order to keep their metallization and thus the effort required for demetallization small.
  • At least the surfaces of the running surfaces 4 of the contact wheels 2 are made of the above-described materials, composites and / or electrically conductive coatings.
  • the almost non-oxidizing material stainless steel with its good contact properties in the electrolyte is preferably used. If necessary, this can be provided with a noble metal coating or with the highly abrasion-resistant electrically conductive diamond coating.
  • the contact wheels 2 are suitable as materials, eg. As with special electrolytes, and the oxidizing metals titanium, niobium and tantalum. In this case, to reduce the contact resistance is basically recommended a coating with an electrically conductive material.
  • About the contact wheel 2 is in the transport direction or transverse to the transport direction of the goods a flow, z. B.
  • etching electrolyte 9 flows in the region of each contact wheel 2, at least one opening 7, z. B. as a nozzle which is directed against the tread 4 of the contact wheel 2.
  • etching electrolyte 9 flows in the spray tube 6, under pressure generated by an electrolyte requester. This has a corrosive property with respect to the metallization of the contact wheel 2 that took place in the electrolytic cell 8.
  • the etching electrolyte 9 may have other properties due to certain chemical additives or ingredients and / or physical states, in particular etching, than the electrolyte 10, which is located in the working container in the local electrolytic cell 8. Among the special physical properties that can take the ⁇ tzelektrolyt 9, z.
  • the pressure in the on-flow element can be adjusted to the required etching rate. He can z. B. at a bar. Prefers are set up to 10 bar. In the case of rigid contact means, high-pressure pumps and nozzles for up to 100 bar for the etching electrolyte 9 can also be used if required.
  • a combination of these two physical measures is even more effective in increasing the etch rate.
  • This physically enhanced etching rate can be further increased by chemical substances with etching properties with regard to the metallization, which are metered or seeded into the etching electrolyte circuit or into the partial flow.
  • the flow arrows 11 indicate the flow directions of the liquids.
  • the ⁇ tzelektrolyt 9 passes after the flow of the contact wheels 2 in the working container 21 located in the electrolyte and mixes with this, optionally after flowing through a filter section. This closes the partial flow circuit of the etching electrolyte 9, which has its beginning in a sump. There also starts the generally much larger circuit of the electrolyte with a much larger volume flow, which is required for swelling of the material for the electroplating process. In exceptional cases, if only a slight movement of electrolyte on the surface of the material to be treated 1 is required, can be dispensed with the large electrolyte circuit.
  • the intensive flow of the contact wheels 2 then causes the low electrolyte movement on the surface of the material during mixing of the electrolytes.
  • the etching electrolyte 9 is z. B. by means of an electrolyte conveyor, consisting of at least one ⁇ tzelektrolytpumpe 12, tubes 30 and 6 spray tubes with openings 7 or nozzles to the contact wheel 2 promoted. With increasing pressure in the spray tube 6, a more intensive and thus more effective etching of the tread 4 to be demolded takes place. Depending on the contact wheel 2, a plurality of openings 7 or nozzles can be directed against the tread 4 to increase the etching time per revolution of the contact wheel 2 increase.
  • the level 1 13 of the electrolyte 10 must extend at least to over the anode 14, as shown in FIG.
  • the upper portion of the contact wheel 2 is then completely outside the electric field of the electrolytic cell 8. If the top, as shown and the bottom of the goods 1 are galvanized, then the lower contact wheels 2 are always completely in the electrolyte 10.
  • the lower spray pipe 6. This corresponds to the level II 16 at the top of the goods 1, ie all participating resources are located in the electrolyte 10. So in this case the electric field, which emanates from the anode 14, not the entire contact wheel 2 detected and metallized, this is largely kept away from the contact wheels 2 by electrically insulating shields 17.
  • the shields 17 are preferably mechanically connected to the spray tube 6. They also serve as splash protection during the intensive flow of the etching electrolyte 9 to the contact wheels. 2
  • the tread 4 of the contact wheel 2 rolls on the estate 1. If the material 1 is sheet-shaped conductor foils, they could adhere to the contact wheels 2 or running surfaces of the contact wheels and thereby lead to a jam in the continuous system. Therefore, this shield 17 is arranged at least on one side on the contact wheel in an illustrated edge contact of the goods 1 along the entire continuous system. This avoids any tripping edges and the adhesion of films to the contact wheels. The shields 17 strip adhering to the contact wheel 2 films. Overall, this results in addition to a good electrical contact a very reliable transport of the goods 1 through the continuous system.
  • the anode 14 may be a soluble anode, e.g. B. act to a plate anode or bulk material in suitable anode baskets.
  • insoluble anodes for. B. from an expanded metal mesh.
  • This expanded metal mesh consists z.
  • the z. B. consists of a noble metal or iridium oxide.
  • the invention is suitable for galvanizing by means of rectifiers for direct current and for bipolar pulse current.
  • bipolar pulse current which is also referred to as reverse pulse current
  • the contact wheel 2 is predominantly poled cathodically, which corresponds to a direct current with respect to the metallization and demetallization, which has a slightly smaller average than the peak value of the cathodic current pulse.
  • FIG. 1 shows the polarities of the bath current supply source, not shown, for direct current or for the predominant polarity in the case of bipolar pulse current.
  • a rectifier and an anode are associated with a plurality of cathodic contact wheels 2 in a continuous system.
  • the Entmetallmaschine invention must be adjusted so effectively that with each revolution of the contact wheels 2 they are completely demetallized.
  • a certain Entmetallticiansreserve should be provided. The reserve is not required if each contact a correspondingly smaller dimensioned rectifier is assigned with preferably common anode. Thus, each contact current is set by the rectifier exactly to the intended target value.
  • Figure 2 shows in cross-section a typical continuous plating plant, as they are for.
  • B. is used in printed circuit board technology.
  • the material 1 is transported vertically into the plane of the drawing.
  • Serve for this purpose are the driven shafts 3, on which contact wheels 2 and transport wheels 18 are located.
  • the soluble anodes 14 in the vicinity of the cathodically poled material 1 form together with this the electrolytic cell 8, in which the flowing electrolyte 10 is located.
  • the circulation of the electrolyte 10 through these electrolytic cells 8 takes place by means of the circulation pump 19.
  • These or more such circulation pumps 19 feed the upper and lower still 20 or other electrolyte flow elements for exchange of the electrolyte in the upper and lower electrolytic cells 8.
  • the electrolyte 10th leaves the working container 21 via z. B.
  • a portion of the electrolyte is promoted according to the invention in a partial circuit and arrives as an etching electrolyte 9 to the surface of the contact wheels 2 to be demolded, which are located in the working container 21.
  • Another pump which is referred to as ⁇ tzelektrolytpumpe 12.
  • This ⁇ tzelektrolytpumpe 12 is dimensioned to increase the etching effect in their performance so that the ⁇ tzelektrolyt 9 is preferably intensively flowed under high pressure to be demolded tread 4 of the contact wheels 2.
  • the tread 4 has a much smaller surface compared to Good 1. Therefore, a smaller volume flow is required for the etching electrolyte 12 than for the electrolyte 10, which flows to the material 1 to be electroplated.
  • the partial flow ie the etching electrolyte 9, z. B. in a water heater 25 far above the working temperature of the electrolyte 10 are also heated.
  • This partial flow usually has only a small proportion of the total circulated in the electrolyte. Therefore, this additional heating, as well as other conditioning measures, for the electroplating process is not disturbing.
  • a common pump can be used with downstream adjustable multi-way valves. All pumps can be controlled in their flow rate, z. B. by means of frequency converter.
  • FIG. 3 shows an enlargement of the device according to the invention through an injection point 26 with a metering pump 27 on the partial circuit of the etching electrolyte 9.
  • suitable substances can be added thereto. Suitable for this purpose, on the one hand all substances that must be continuously replenished for reasons of consumption by the electroplating process and by the carryover through the good and a corrosive property with respect to the
  • Electroplating process have deposited metal.
  • these substances initially have a substantially higher concentration than in the general electrolyte 10, in which the partial flow passes after passing through the contact wheels 2 to be demetallised.
  • the higher concentration increases the etch rate of the etching electrolyte 9.
  • chlorine which is required for other reasons in sulfuric acid copper baths as an additive.
  • suitable materials for seeding are those which rapidly disintegrate in the electrolyte and do not interfere with the electrolytic process, but have previously had a corrosive effect on the metal deposited during the galvanizing process.
  • An example of this is weak or strong oxidants, such as. As ozone, atmospheric oxygen, oxygen or hydrogen peroxide.
  • the electrolyte conveying device is correspondingly dimensioned. This means an adjustment of the flow velocity in the tubes 6, 30 and their length from the injection point 26 to the contact wheels 2.
  • the subcircuit, which leads the etching electrolyte 9, are heated by means of a heater 25.
  • FIG. 4 shows electrolytic cells 8 with upper and lower electrodes as insoluble anodes 14.
  • the requisite continuous metal supplementation takes place in a regeneration space 28 in which the regeneration metal 29 to be dissolved is in the form of metal pieces 29.
  • the electrolyte has u. a. as a result of ingested atmospheric oxygen a corrosive property with respect to the metal to be deposited. If the surface area of the metal pieces 29 is sufficiently large and the electrolyte 10 flows through the regeneration space 28, the copper content of the electrolyte for the galvanizing process can be maintained.
  • This electrolyte 10 also has a corrosive effect on the copper-plated surface of the contact wheels 2 in the partial circuit as the etching electrolyte 9.
  • the partial flows can be heated by means of heaters 25 to increase the etching rate.
  • the circulation promotion of the electrolyte 10 closes by the flow through the working container 21 and through the regeneration space 28th
  • the metal content of a copper electrolyte may, for. B. also be kept constant by a continuous supplement with copper oxide.
  • the electrolyte a redox system with a redox agent, for. As iron can be added.
  • the oxidized to the anodes 14 redox agent, namely Fe 3+ has a strong corrosive property with respect to copper.
  • the electrolyte 10 enriched with the Fe 3+ ions is conducted from the vicinity of the place of origin, namely the anodes 14, into the pump sump 24. This happens from the working container 21 via the overflows 22 overflowing and expiring through the outlets 23.
  • Figures 2 to 4 show by examples of printed circuit boards or conductor foils pass-galvanizing with a flat Good 1.
  • the electrical contacting of the goods 1 takes place here at its two edges. This improves the layer thickness distribution of the metallization transversely to the transport direction. However, this presupposes that the material 1 always has the same dimensions at least transversely to the transport direction. Is to be expected in a continuous galvanizing with different dimensions of the material to be plated, then the one-sided contact at the top and / or at the bottom of a contact track of the goods provided.

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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)
  • Electroplating Methods And Accessories (AREA)
  • Manufacture Of Switches (AREA)

Abstract

L'invention concerne la mise en contact électrique d'un article (1) sous forme de plaquette ou en bande, qui est acheminé sur une bande transporteuse à l'aide de moyens de transport et/ou de contact rotatifs (2) à travers une installation de galvanisation en continu. Les moyens de contact (2) polarisés cathodiquement se trouvent dans l'électrolyte (10) au niveau de l'article (1) ou sur ce dernier. A chaque tour, les moyens de contact (2) rigides ou élastiques sont également métallisés comme l'article (1). Cette métallisation doit être retirée en continu des roues de contact (2). A cet effet, selon l'invention, une partie de l'électrolyte (10) extrait du récipient de travail et recyclé est dérivée pour être utilisée comme électrolyte d'attaque (9). Cet électrolyte d'attaque (9) est conditionné physiquement et/ou chimiquement de manière à présenter une vitesse d'attaque accrue par rapport au métal déposé. L'électrolyte est injecté de manière intense sur les surfaces à démétalliser des roues de contact (2), ces surfaces étant ainsi démétallisées en continu sans courant externe dans le récipient de travail.
PCT/DE2010/000593 2009-05-22 2010-05-18 Dispositif et procédé de mise en contact électrique d'un article dans des installations de galvanisation Ceased WO2010133221A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102009023767.4 2009-05-22
DE102009023767A DE102009023767A1 (de) 2009-05-22 2009-05-22 Vorrichtung und Verfahren zum elektrischen Kontaktieren von Gut in Galvanisieranlagen

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WO2010133221A2 true WO2010133221A2 (fr) 2010-11-25
WO2010133221A3 WO2010133221A3 (fr) 2011-05-19

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WO (1) WO2010133221A2 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114411217A (zh) * 2021-12-23 2022-04-29 河南特防建设集团有限公司 一种金属材料腐蚀设备
CN116516450A (zh) * 2023-04-12 2023-08-01 福建金石能源有限公司 一种无接触式水平电镀装备

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DD215589A1 (de) 1983-05-11 1984-11-14 Leipzig Galvanotechnik Verfahren zur elektrolytischen metallabscheidung bei erzwungener konvektion

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DE102005033784A1 (de) * 2005-07-20 2007-01-25 Viktoria Händlmeier System zur galvanischen Abscheidung einer leitfähigen Schicht auf einem nichtleitfähigen Trägermaterial

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114411217A (zh) * 2021-12-23 2022-04-29 河南特防建设集团有限公司 一种金属材料腐蚀设备
CN114411217B (zh) * 2021-12-23 2023-07-07 河南特防建设集团有限公司 一种金属材料腐蚀设备
CN116516450A (zh) * 2023-04-12 2023-08-01 福建金石能源有限公司 一种无接触式水平电镀装备

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DE102009023767A1 (de) 2010-11-25

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