EP0699781B1 - Electrolytic process for treating, particularly continuously plating a substrate - Google Patents
Electrolytic process for treating, particularly continuously plating a substrate Download PDFInfo
- Publication number
- EP0699781B1 EP0699781B1 EP95112519A EP95112519A EP0699781B1 EP 0699781 B1 EP0699781 B1 EP 0699781B1 EP 95112519 A EP95112519 A EP 95112519A EP 95112519 A EP95112519 A EP 95112519A EP 0699781 B1 EP0699781 B1 EP 0699781B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- electrolyte
- fact
- nozzle body
- coated
- flow
- 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.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims description 23
- 238000007747 plating Methods 0.000 title 1
- 239000000758 substrate Substances 0.000 title 1
- 239000003792 electrolyte Substances 0.000 claims description 37
- 238000009792 diffusion process Methods 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 13
- 239000011248 coating agent Substances 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 239000012811 non-conductive material Substances 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000004020 conductor Substances 0.000 claims description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 2
- 230000004075 alteration Effects 0.000 claims 1
- 238000005507 spraying Methods 0.000 claims 1
- 239000000463 material Substances 0.000 description 9
- 230000008021 deposition Effects 0.000 description 8
- 238000005246 galvanizing Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 238000009713 electroplating Methods 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000013598 vector Substances 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
Images
Classifications
-
- 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
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
-
- 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
- C25D7/04—Tubes; Rings; Hollow bodies
Definitions
- the invention relates to a galvanic method for galvanic or chemical treatment, in particular for the continuous application of metallic layers on a body according to the generic term of Claim 1, and a device for Execution of the procedure.
- the current density deposition rate curve therefore has an asymptotic limit, which, as mentioned, arises from the electrically insulating diffusion layer when there is insufficient supply of material. This can be remedied by moving the electrolyte. As experiments have shown, the diffusion layer thickness decreases with increasing intensity of the electrolyte movement. On the other hand, metallic precipitates become rough and powdery when current densities are chosen that approach the theoretically possible limit current densities. In order to obtain perfect coating qualities, current densities must therefore be selected that are far below the possible limit current density and are usually only about a third of the limit current density.
- a method is known from DE 34 39 750 A1, at to increase the separation speed of electroplating coating materials Electrolyte solution in the opposite direction to the direction of movement of the body to be coated is moved, the itself from the two differential speeds resulting overall speed at the surface of the body to be coated in the area of turbulent Current lies.
- the object of the invention is to remedy this through an improved galvanic process, as well by a device for performing the method, to enable both the diffusion layer between the electrolyte and the body to be coated almost completely dissolve as well asymptotic limit of the deposition rate curve to move up to the Significantly reduce coating time and the To improve the quality of the metal coating.
- This task is for the procedure by characteristic features of claim 1 and for the device by the characteristic features of claim 2 solved.
- the method according to the invention is made possible by a almost complete dissolution of the diffusion layer increase the deposition rate while at the same time Improvement of the coating quality in the chosen Working area of the current density deposition rate curve.
- the body to be treated is flowed uniformly from all sides irrespective of the size of its diameter and its surface quality.
- the gradual partial change in the flow along the body not only eliminates a pressure drop of the injected electrolyte with respect to the length of the body under load, but also, seen from the galvanizing process, produces an electrical current flow which has a pulsating effect on the body.
- the orifices act as throttling points at which the flow speed increases, which has an effect on the material transport as an increase in current.
- Both the directional, high-speed all-round inflow of the body, as well as the partial change in the flow rate have the effect that the diffusion layer along the body surface mentioned is almost completely destroyed, so that an undisturbed transport of material to the cathode is ensured.
- the flow effect of the orifices also automatically centers the body to be treated in the nozzle body, so that a uniform geometric distance between the body and the inner wall of the nozzle body is ensured. Uniform layer thicknesses are achieved and short circuits avoided. In addition, it is ensured that the metal coating applied to the body is not mechanically damaged.
- the prior art processes for galvanizing for example in galvanizing, have a maximum current density of 80 to 90 A / dm 2 on the surface of a body to be coated
- the method according to the invention for example also in galvanizing, has a current density of 10 up to 400 A / dm 2 .
- the deposition rate is therefore approximately 3.5 times higher than that measured in the prior art.
- the non-metallic, electrically non-conductive Material such as plastic or ceramic existing Panels in the form of washers enable you to choose the mutual distance and the inner diameter taking into account the diameter of the Exit openings of the holes and their number - Volume throughput of the electrolyte - and its strength the pulse width and pulse rate of the towards galvanizing body acting electrical To determine current flow optimally.
- electrically conductive material of the panels other electric fields in the electrolyte and therefore also other types of coating. With alternating The same applies to arranged blend materials. In this way, as experiments have shown, Metal alloys, as well as predeterminable microstructures to be galvanically deposited, as was previously not possible was.
- Metal layer or its layer thickness can be any many devices according to the invention in a row horizontally connected in series.
- a method has become known from DE 33 17 970 A1 of electrolytically locally coating a printed circuit board by means of an electrolyte emerging from two opposing nozzles; see. there page 7, lines 11 to 13.
- the circuit board is guided past the nozzles in a manner similar to wave soldering, for which purpose the electrolyte is fed from a trough to the nozzles and is discharged from them.
- the nozzles are used solely for the targeted partial coating of the printed circuit boards and not for increasing the exit speed of the electrolyte, so that the problem of the dissolution of a diffusion layer due to an end speed of the electrolyte adding up from speed vectors to produce a turbulent flow was not addressed there and therefore not given is.
- FIG. 1 is in a process trough 10 a working container 12 for receiving still too descriptive devices 14 for electroplating or chemical treatment, according to the embodiment for continuous application of a metal layer one through the working tank 12 and the Devices 14 continuously guided - here rod-shaped - body 15.
- a pump 16 is used in the process tub 10 located electrolyte 18 via a pump line 19 and each have the shape of a pipe socket Feeder 20 of the individual device 14 is fed.
- the escaping electrolyte flows in the direction of the Arrows 17 back into the process tub 10.
- the flow rate of the electrolyte can be pumped be influenced.
- FIG. 2 One of the devices 14 is enlarged in FIG. 2 shown. As shown there, this flows through the Feeder 20 introduced electrolyte 18 the device 14 and thereby arrives via a hollow body 30 to be described in a nozzle body 34 and there, as the individual arrows show, in the Work container 12 and from there into the process tub 10 back.
- the one designated overall by reference number 14 Device for the continuous electroplating of Wires, pipe outer surfaces or similar bodies 15 includes, as shown in Figures 2 and 3, the dated Electrolyte 18 flooded, forming a pressure vessel Hollow body 30 with two end faces 31 and 32 and the nozzle body 34 formed as a hollow body, the is arranged coaxially to the hollow body 30.
- Nozzle body 34 and hollow body 30 have a common centric Through opening 35.
- the nozzle body 34 is on all sides with an insoluble metal layer 38 of a metal coated from the platinum group.
- This layer of metal 38 also covers the end faces 31 and 32 and the inner surface of the hollow body 30, and has a Thickness from 2 to 20 ⁇ .
- the through hole 35 marked with the metal layer 38 is to this This ensures that the effective areas of the Nozzle body 34 no metal ions to the electrolyte 18 submit.
- the nozzle body 34 has over its entire circumference distributes a plurality of equally spaced in With respect to the longitudinal axis 16 perpendicular to it Cross-sectional areas 11 distributed holes 44, each at the same angle ⁇ obliquely to and against the direction of flow and by one Swirl angle ⁇ inclined - cf. Figure 3 and 4 - the middle through the nozzle body 34 to be coated Body 15 run.
- On the exit side 25 of the Nozzle body 34 is an electrically non-conductive Guide ring 26 arranged.
- FIG. 3 shows, the axis of symmetry 41 of the Pipe socket 20 parallel and eccentric around one Distance a to the transverse axis 40 of the device 14 is offset.
- the result of this is that it is in the hollow body 30 pumped electrolyte 18 in its flow behavior enters the hollow body 30 as undisturbed as possible and flows around the nozzle body 34.
- the openings of the influence Bores 44 are each on flanks 46 of the Outer surface of the nozzle body 34, each part of evenly one behind the other Cross-section V-shaped constrictions 47 are.
- the pumped electrolyte 18 flows into it Constrictions 47 and from there without loss of pressure in the Bores 44 and as Laval nozzles acting outlet openings 37 in the space of Through opening 35.
- In the through opening 35 of the Nozzle body 34 are - to the cross-sectional areas 11 offset in the longitudinal direction - the longitudinal axis 16 perpendicular intersecting planes A to E, aperture 36 inserted each have a passage opening 37.
- FIG. 4 shows one of the diaphragms 36 made of electrically non-conductive material.
- these screens 36 can also consist of an electrically conductive material, or can be arranged alternately of electrically conductive and non-conductive material.
- the flow opening 37 of the orifices 36 are gradually enlarged with respect to the flow direction of the electrolyte, which is opposite to the flow direction of the body 15 to be coated, in order to prevent a pressure drop in the nozzle body 34.
- the smallest flow opening 37 is therefore in level E, while the largest flow opening 37 is in level A.
- the diaphragms 36 have a plurality of swirl-generating incisions 39 which are oriented tangentially to the passage opening 37.
- the operation of the described device is as follows:
- the body 15 to be coated is connected to a power source, not shown, at its negative pole, for example via current-carrying contact rollers, while the nozzle body 34 is connected to the positive pole of the power source, not shown, via busbars 13.
- the current density is adjusted to 10 to 400 A / dm 2 using circuit elements known per se in accordance with the method to be carried out.
- the natural speed impressed on the body 15 to be coated acts in the direction of passage.
- the electrolyte 18 moved by the pump 16 is accelerated as it flows through the bores 44, since these act as Laval nozzles, and is injected at an angle ⁇ obliquely to and against the direction of flow of the body 15 to be coated and at the twist angle ⁇ .
- the uniform arrangement of the bores 44 in the nozzle body 34 ensures a uniform impact of the electrolyte 18 on the entire surface of the body 15 to be coated and moving against the flow direction.
- the oppositely directed movement vectors of the body 15 and the injected electrolyte 18 add up and, under the beam effect of the bores 44 on the surface of the body 15 to be coated, cause a turbulent flow around the entire surface. This turbulent flow almost completely destroys the diffusion layer created during the galvanization.
- the diaphragms 36 with their stepped passage openings 37 arranged between the respective area planes 11 of the bores 44 the pressure of the electrolyte 18 in the nozzle body 34 is kept constant over its entire length.
- these diaphragms act as localized rapid currents for the electrolyte 18, so that, viewed from the galvanizing process, a current flow which has a pulsating effect on the body 15 is generated.
- the guide ring 26 has the task of a short circuit to prevent between body 15 and nozzle body 34, which would come about when the body 15 due to the relative movements between body 15 and Electrolyte 18 and those caused thereby Vibrations would touch the nozzle body 34.
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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)
Description
Die Erfindung betrifft ein galvanisches Verfahren zum galvanischen oder chemischen Behandeln, insbesondere zum kontinuierlichen Aufbringen metallischer Schichten auf einen Körper nach dem Oberbegriff des Patentanspruches 1, sowie eine Vorrichtung zur Durchführung des Verfahrens.The invention relates to a galvanic method for galvanic or chemical treatment, in particular for the continuous application of metallic layers on a body according to the generic term of Claim 1, and a device for Execution of the procedure.
Aus der Theorie ist es bekannt, daß beim
elektrolytischen Stofftransport die Abscheidungsrate
mit ansteigenden Stromdichten proportional zunimmt. In
der Praxis jedoch entsteht an der Kathode bei
ansteigenden Stromdichten eine Diffusionsschicht, da
der Materietransport zwischen Anode und Kathode
langsamer ist als die Niederschlagsgeschwindigkeit der
Ionen in unmittelbarer Nähe der Kathode. Je größer also
die angelegte Stromdichte gewählt wird, desto größer
ist die Diffusionsschicht um die Kathode und desto
langsamer und unvollständiger ist die Abscheidungsrate
der Ionen auf die Kathode. Ab einer bestimmten
Reaktionsgeschwindigkeit kann das Nachliefern von
Metallionen an die Phasengrenze zwischen den Bereichen
Materietransport und Ladungsdurchtritt das Konsumieren
an der Kathode nicht mehr ausgleichen. Die Stromdichte-Abscheidungsrate-Kurve
weist daher einen asymptotischen
Grenzwert auf, der, wie erwähnt, durch die elektrisch
isolierende Diffusionsschicht bei ungenügendem
Nachschub von Materie entsteht. Abhilfe kann durch
Elektrolytbewegung geschaffen werden.
Wie Versuche gezeigt haben, nimmt mit zunehmender
Intensität der Elektrolytbewegung die
Diffusionsschichtdicke ab.
Andererseits werden metallische Niederschläge rauh und
pulverig, wenn Stromdichten gewählt werden, die sich
den theoretisch möglichen Grenzstromdichten nähern. Zur
Gewinnung einwandfreier Überzugsqualitäten sind daher
Stromdichten zu wählen, die weit unter der möglichen
Grenzstromdichte liegen und in der Regel ca. nur ein
Drittel der Grenzstromdichte betragen.It is known from theory that in electrolytic mass transport the deposition rate increases proportionally with increasing current densities. In practice, however, a diffusion layer is formed on the cathode with increasing current densities, since the material transport between the anode and cathode is slower than the rate of precipitation of the ions in the immediate vicinity of the cathode. The greater the current density selected, the larger the diffusion layer around the cathode and the slower and incomplete the rate of ion deposition on the cathode. Above a certain reaction speed, the subsequent supply of metal ions to the phase boundary between the areas of material transport and charge passage can no longer compensate for the consumption at the cathode. The current density deposition rate curve therefore has an asymptotic limit, which, as mentioned, arises from the electrically insulating diffusion layer when there is insufficient supply of material. This can be remedied by moving the electrolyte. As experiments have shown, the diffusion layer thickness decreases with increasing intensity of the electrolyte movement.
On the other hand, metallic precipitates become rough and powdery when current densities are chosen that approach the theoretically possible limit current densities. In order to obtain perfect coating qualities, current densities must therefore be selected that are far below the possible limit current density and are usually only about a third of the limit current density.
Insbesondere bei der Zinkabscheidung führt eine erhöhte
Stromdichte bedingt durch die vorhandene
Diffusionsschicht und dem damit verbundenen schlechten
Materieaustausch zu unbrauchbaren Zinkniederschlägen am
zu beschichtenden Körper. Sollte zusätzlich zu den
Zinkionen im Elektrolyt eine Zinkanode Verwendung
finden, um den prozentualen Anteil der Metallionen für
die Dauer der Galvanisierung konstant zu halten, treten
an der Zinkanode Passivitätserscheinungen auf, da die
anodische Stromdichte aufgrund des Auflösungsprozeßes
an der Anode ansteigt.
Eine beidseitige Anordnung von Metallanoden zur Kathode
hilft ebenfalls nicht weiter, da dann exzentrische
Niederschläge produziert werden.In the case of zinc deposition in particular, an increased current density due to the existing diffusion layer and the associated poor material exchange leads to unusable zinc deposits on the body to be coated. If, in addition to the zinc ions in the electrolyte, a zinc anode is used to keep the percentage of metal ions constant for the duration of the galvanization, passivity phenomena occur at the zinc anode, since the anodic current density increases due to the dissolution process at the anode.
An arrangement of metal anodes on both sides to the cathode also does not help, since eccentric precipitation is then produced.
Aus der DE 34 39 750 A1 ist ein Verfahren bekannt, bei
dem zur Erhöhung der Abscheidegeschwindigkeit von
galvanisch aufzubringenden Beschichtungsmaterialien die
Elektrolytlösung in Gegenrichtung zur Bewegungsrichtung
des zu beschichtenden Körpers bewegt wird, wobei die
sich aus den beiden Differenzgeschwindigkeiten
ergebende Gesamtgeschwindigkeit an der Oberfläche des
zu beschichtenden Körpers im Bereich der turbulenten
Strömung liegt.A method is known from
Auf diese Weise wird zwar durch eine turbulente Strömung die Diffusionsschichtdicke reduziert, jedoch gelingt damit der Abbau der Diffusionschicht nicht ausreichend. Dies zeigt sich z. B. bereits daran, daß dort für die anzulegende Stromdichte eine Obergrenze von 80 bis 90 A/dm2 nicht überschritten werden darf. Am zu beschichtenden Körper ist daher dort weiterhin eine Diffusionsschicht von 10 bis 15 µm vorhanden. In this way, the diffusion layer thickness is reduced by a turbulent flow, but the degradation of the diffusion layer is not sufficiently successful. This shows z. B. already remember that an upper limit of 80 to 90 A / dm 2 must not be exceeded there for the current density to be applied. A diffusion layer of 10 to 15 μm is therefore still present on the body to be coated.
Aufgabe der Erfindung ist es, hier Abhilfe zu schaffen durch ein verbessertes galvanisches Verfahren, sowie durch eine Vorrichtung zur Durchführung des Verfahrens, um zu ermöglichen, sowohl die Diffusionsschicht zwischen Elektrolyt und zu beschichtendem Körper annähernd vollständig aufzulösen, als auch den asymptotischen Grenzwert der Abscheidungsrate-Kurve nach oben zu verschieben, um damit die Beschichtungszeit erheblich zu reduzieren und die Qualität der Metallbeschichtung zu verbessern.The object of the invention is to remedy this through an improved galvanic process, as well by a device for performing the method, to enable both the diffusion layer between the electrolyte and the body to be coated almost completely dissolve as well asymptotic limit of the deposition rate curve to move up to the Significantly reduce coating time and the To improve the quality of the metal coating.
Diese Aufgabe ist für das Verfahren durch die kennzeichnenden Merkmale des Patentanspruches 1 sowie für die Vorrichtung durch die kennzeichnenden Merkmale des Patentanspruches 2 gelöst.This task is for the procedure by characteristic features of claim 1 and for the device by the characteristic features of claim 2 solved.
Weitere Merkmale der Erfindung ergeben sich aus den Unteransprüchen.Further features of the invention result from the Subclaims.
Das erfindungsgemäße Verfahren ermöglicht durch ein annähernd vollständiges Auflösen der Diffusionsschicht die Abscheidungsrate zu erhöhen bei gleichzeitiger Verbesserung der Überzugsqualität im gewählten Arbeitsbereich der Stromdichte-Abscheidungsrate-Kurve.The method according to the invention is made possible by a almost complete dissolution of the diffusion layer increase the deposition rate while at the same time Improvement of the coating quality in the chosen Working area of the current density deposition rate curve.
Infolge der erfindungsgemäßen Ausbildung des als
unlösliche Anode wirkenden Düsenkörpers sowie der
Drallneigung der Düsen für den Austritt des
Elektrolyten wird der zu behandelnde Körper unabhängig
von der Größe seines Durchmessers und seiner
Oberflächenbeschaffenheit von allen Seiten gleichmäßig
angeströmt. Durch das stufenweise partielle Verändern
der Strömung längs des Körpers wird nicht nur ein
Druckgefälle des eingespritzten Elektrolytes in Bezug
auf die beaufschlagte Länge des Körpers beseitigt,
sondern darüberhinaus vom Galvanisierungsprozeß her
gesehen ein auf den Körper pulsierend wirkender
elektrischer Stromfluß erzielt. Die Blenden wirken
nämlich als Drosselstellen, an denen die
Strömungsgeschwindigkeit zunimmt, was sich in Bezug auf
den Materietransport als Stromerhöhung auswirkt. Sowohl
das gerichtete, mit hoher Geschwindigkeit erfolgende
allseitige Anströmen des Körpers, als auch das
partielle Verändern der Strömungsgeschwindigkeit
bewirken, daß die Diffusionsschicht längs der genannten
Körperoberfläche annähernd vollständig zerstört wird,
so daß ein ungestörter Materietransport zur Kathode
gewährleistet ist.
Über die Strömungswirkung der Blenden erfolgt ferner
eine selbsttätige Zentrierung des zu behandelnden
Körpers im Düsenkörper, so daß ein gleichmäßiger
geometrischer Abstand des Körpers zur
Innenmantelwandung des Düsenkörpers gewährleistet ist.
Gleichmäßige Schichtdicken werden dadurch erzielt und
Kurzschlüsse vermieden. Darüberhinaus wird
sichergestellt, daß der am Körper aufgebrachte
Metallüberzug mechanisch nicht beschädigt wird.As a result of the inventive design of the nozzle body acting as an insoluble anode and the swirl tendency of the nozzles for the outlet of the electrolyte, the body to be treated is flowed uniformly from all sides irrespective of the size of its diameter and its surface quality. The gradual partial change in the flow along the body not only eliminates a pressure drop of the injected electrolyte with respect to the length of the body under load, but also, seen from the galvanizing process, produces an electrical current flow which has a pulsating effect on the body. The orifices act as throttling points at which the flow speed increases, which has an effect on the material transport as an increase in current. Both the directional, high-speed all-round inflow of the body, as well as the partial change in the flow rate have the effect that the diffusion layer along the body surface mentioned is almost completely destroyed, so that an undisturbed transport of material to the cathode is ensured.
The flow effect of the orifices also automatically centers the body to be treated in the nozzle body, so that a uniform geometric distance between the body and the inner wall of the nozzle body is ensured. Uniform layer thicknesses are achieved and short circuits avoided. In addition, it is ensured that the metal coating applied to the body is not mechanically damaged.
Während die zum Stand der Technik zählenden Verfahren zur Galvanisierung, beispielsweise beim galvanischen Verzinken, an der Oberfläche eines zu beschichtenden Körpers eine maximale Stromdichte von 80 bis 90 A/dm2 aufweisen, erlaubt das erfindungsgemäße Verfahren, z.B. ebenfalls beim galvanischen Verzinken eine Stromdichte von 10 bis 400 A/dm2. Die Abscheidungsrate liegt daher, gemessen gegenüber dem Stand der Technik, um ca. das 3,5-fache höher.While the prior art processes for galvanizing, for example in galvanizing, have a maximum current density of 80 to 90 A / dm 2 on the surface of a body to be coated, the method according to the invention, for example also in galvanizing, has a current density of 10 up to 400 A / dm 2 . The deposition rate is therefore approximately 3.5 times higher than that measured in the prior art.
Die aus nichtmetallischen, elektrisch nicht leitendem Material, wie Kunststoff oder Keramik bestehenden Blenden in Form von Ringscheiben ermöglichen durch Wahl des gegenseitigen Abstandes und des Innendurchmessers unter Berücksichtigung der Durchmesser der Austrittsöffnungen der Bohrungen, sowie ihrer Anzahl - Mengendurchsatz des Elektrolyten - sowie deren Stärke die Pulsbreite und Pulsfrequenz des auf den zu galvanisierenden Körpers wirkenden elektrischen Stromflußes optimal zu bestimmen. Bei der Verwendung von elektrisch leitendem Material der Blenden entstehen andere elektrische Felder im Elektrolyt und damit auch andere Beschichtungsarten. Bei alternierend angeordneten Blendmaterialien gilt ähnliches. Auf diese Weise gelingt es, wie Versuche gezeigt haben, Metallegierungen, sowie vorbestimmbare Gefügestrukturen galvanisch abzuscheiden, wie dies bisher nicht möglich war.The non-metallic, electrically non-conductive Material such as plastic or ceramic existing Panels in the form of washers enable you to choose the mutual distance and the inner diameter taking into account the diameter of the Exit openings of the holes and their number - Volume throughput of the electrolyte - and its strength the pulse width and pulse rate of the towards galvanizing body acting electrical To determine current flow optimally. When using of electrically conductive material of the panels other electric fields in the electrolyte and therefore also other types of coating. With alternating The same applies to arranged blend materials. In this way, as experiments have shown, Metal alloys, as well as predeterminable microstructures to be galvanically deposited, as was previously not possible was.
Je nach gewünschter Fertigungszeit sowie Qualität der Metallschicht oder deren Schichtdicke können beliebig viele erfindungsgemäße Vorrichtungen hintereinander liegend in Reihe geschaltet angeordnet werden.Depending on the desired manufacturing time and quality of the Metal layer or its layer thickness can be any many devices according to the invention in a row horizontally connected in series.
Zwar ist aus der DE 33 17 970 A1 ein Verfahren bekannt
geworden, eine Leiterplatte mittels eines aus zwei,
einander gegenüberliegenden Düsen austretenden
Elektrolyten galvanisch örtlich zu beschichten; vgl.
dort Seite 7, Zeilen 11 bis 13.
Zwecks flächiger Beschichtung wird die Leiterplatte
ähnlich wie bei einer Schwallötung an den Düsen
vorbeigeführt, wozu das Elektrolyt aus einer Wanne den
Düsen zugeführt und aus diesen ausgebracht wird. Die
Düsen dienen also allein der gezielten partiellen
Beschichtung der Leiterplatten und nicht der Erhöhung
der Austrittsgeschwindigkeit des Elektrolytes, so daß
das Problem der Auflösung einer Diffusionsschicht durch
eine sich aus Geschwindigkeitsvektoren addierende
Endgeschwindigkeit des Elektrolyten zur Erzeugung
einer turbulenten Strömung, dort nicht angesprochen und
daher auch nicht gegeben ist. A method has become known from DE 33 17 970 A1 of electrolytically locally coating a printed circuit board by means of an electrolyte emerging from two opposing nozzles; see. there page 7,
For the purpose of surface coating, the circuit board is guided past the nozzles in a manner similar to wave soldering, for which purpose the electrolyte is fed from a trough to the nozzles and is discharged from them. The nozzles are used solely for the targeted partial coating of the printed circuit boards and not for increasing the exit speed of the electrolyte, so that the problem of the dissolution of a diffusion layer due to an end speed of the electrolyte adding up from speed vectors to produce a turbulent flow was not addressed there and therefore not given is.
Die Erfindung ist nachfolgend an Hand eines in der
Zeichnung dargestellten Ausführungsbeispieles
beschrieben.
Im einzelnen zeigen:
- Fig. 1
- eine Anordnung zum Galvanisieren mit einer Vorrichtung gemäß der Erfindung,
- Fig. 2
- einen Längsschnitt durch ein Ausführungsbeispiel einer Vorrichtung zur Durchführung des Verfahrens nach der Erfindung, mit einem eine zentrale Durchgangsbohrung und in den dazu orthogonalen Bereichsebenen eine Mehrzahl von Düsenbohrungen aufweisenden Düsenkörper, der einen zu beschichtenden Körper umfaßt und mit einem der Zuführung von Elektrolyt dienenden Hohlkörper,
- Fig. 3
- eine Frontansicht der Vorrichtung nach Figur 2 und
- Fig. 4
- eine Einzelheit aus Figur 2 in vergrößerter Darstellung.
In detail show:
- Fig. 1
- an arrangement for electroplating with a device according to the invention,
- Fig. 2
- 2 shows a longitudinal section through an exemplary embodiment of a device for carrying out the method according to the invention, with a nozzle body having a central through-bore and in the region planes orthogonal thereto a plurality of nozzle bores, which comprises a body to be coated and with a hollow body serving for supplying electrolyte,
- Fig. 3
- a front view of the device of Figure 2 and
- Fig. 4
- a detail of Figure 2 in an enlarged view.
Wie Figur 1 zeigt, befindet sich in einer Prozesswanne
10 ein Arbeitsbehälter 12 zur Aufnahme von noch zu
beschreibenden Vorrichtungen 14 zum Galvanisieren oder
chemischen Behandeln, nach dem Ausführungsbeispiel zum
kontinuierlichen Aufbringen einer Metallschicht auf
einen durch den Arbeitsbehälter 12 und die
Vorrichtungen 14 kontinuierlich geführten - hier
stabförmig ausgebildeten - Körper 15. As shown in Figure 1, is in a process trough
10 a working
Über eine Pumpe 16 wird ein in der Prozeßwanne 10
befindliches Elektrolyt 18 über eine Pumpleitung 19 und
jeweils eine die Form eines Rohrstutzens aufweisende
Zuführung 20 der einzelnen Vorrichtung 14 zugeführt.
Das austretende Elektrolyt fließt in Richtung der
Pfeile 17 in die Prozeßwanne 10 zurück. Die Strömungsgeschwindigkeit
des Elektrolyts kann über die Pumpe
beinflußt werden.A
Eine der Vorrichtungen 14 ist in Figur 2 vergrößert
dargestellt. Wie dort gezeigt, durchströmt das über die
Zuführung 20 eingeleitete Elektrolyt 18 die Vorrichtung
14 und gelangt dabei über einen Hohlkörper 30 in noch
zu beschreibender Weise in einen Düsenkörper 34 und von
dort, wie die einzelnen Pfeile zeigen, wieder in den
Arbeitsbehälter 12 und von dort in die Prozeßwanne 10
zurück.One of the
Die insgesamt mit der Bezugsziffer 14 bezeichnete
Vorrichtung zur kontinuierlichen Galvanisierung von
Drähten, Rohraußenflächen oder ähnlichen Körpern 15
umfaßt, wie die Figuren 2 und 3 zeigen, den vom
Elektrolyt 18 durchfluteten, einen Druckbehälter bildenden
Hohlkörper 30 mit zwei Stirnseiten 31 und 32 und
den als Hohlkörper ausgebildeten Düsenkörper 34, der
koaxial zum Hohlkörper 30 angeordnet ist. Düsenkörper
34 und Hohlkörper 30 haben eine gemeinsame zentrische
Durchgangsöffnung 35. Der Düsenkörper 34 ist allseitig
mit einer unlöslichen Metallschicht 38 eines Metalles
aus der Platingruppe beschichtet. Diese Metallschicht
38 überdeckt auch die Stirnseiten 31 und 32 sowie die
innere Mantelfläche des Hohlkörpers 30, und hat eine
Dicke von 2 bis 20 µ. Wie die Figur 2 zeigt, ist der
Übersichtlichkeit halber nur die Durchgangsbohrung 35
mit der Metallschicht 38 gekennzeichnet. Auf diese
Weise ist sichergestellt, daß die wirksamen Flächen des
Düsenkörpers 34 keine Metallionen an das Elektrolyt 18
abgeben.The one designated overall by
Mit der Mantelfläche des Hohlkörpers 30 ist die
Zuführung 20 verbunden, die als tangential einmündender
- vgl. Figur 3 - Rohrstutzen 24 ausgebildet ist, der
über eine Überwurfmutter 23 mit einem Flansch 22 der
Pumpleitung 19 verbunden ist. Zwischen dem Flansch 22
und dem Rohrstutzen 24 ist eine O-Ring-Dichtung 25
angeordnet. Die Pumpenleitung 19 ist daher lösbar aber
dichtend mit dem Rohrstutzen 24 verbunden.With the outer surface of the
Der Düsenkörper 34 weist über seinen gesamten Umfang
verteilt eine Mehrzahl von in gleichen Abständen in
Bezug auf die Längsachse 16 senkrecht dazu verlaufenden
Querschnittsbereichen 11 verteilt angeordnete Bohrungen
44 auf, die jeweils in gleichen Winkeln α schräg zur
und entgegen der Durchlaufrichtung sowie um einen
Drallwinkel β geneigt - vgl. Figur 3 und 4 - des mittig
durch den Düsenkörper 34 geführten, zu beschichtenden
Körpers 15 verlaufen. An der Austrittsseite 25 des
Düsenkörpers 34 ist ein elektrisch nicht leitender
Führungsring 26 angeordnet.The
Wie Figur 3 zeigt, ist die Symmetrieachse 41 des
Rohrstutzens 20 parallel und exzentrisch um einen
Abstand a zur Querachse 40 der Vorrichtung 14 versetzt.
Dies hat zur Folge, daß das in den Hohlkörper 30
eingepumpte Elektrolyt 18 in seinem Strömungsverhalten
möglichst ungestört in den Hohlkörper 30 eintritt und
um den Düsenkörper 34 strömt. Die Einflußöffnungen der
Bohrungen 44 liegen jeweils auf Flanken 46 der
Außenmantelfläche des Düsenkörpers 34, die jeweils Teil
von gleichmäßig hintereinander liegenden, im
Querschnitt V-förmigen Einschnürungen 47 sind.
Das eingepumpte Elektrolyt 18 strömt in diese
Einschnürungen 47 und von dort ohne Druckverlust in die
Bohrungen 44 ein sowie über die als Lavaldüsen
wirkenden Austrittsöffnungen 37 in den Raum der
Durchgangsöffnung 35. In die Durchgangsöffnung 35 des
Düsenkörpers 34 sind - zu den Querschnittsbereichen 11
in Längsrichtung versetzt - die Längsachse 16 senkrecht
schneidende Ebenen A bis E, Blenden 36 eingefügt, die
jeweils eine Durchlaßöffnung 37 aufweisen.As FIG. 3 shows, the axis of
In Figur 4 ist eine der aus elektrisch nicht leitendem
Material bestehenden Blenden 36 dargestellt. Für
bestimmte Anwendungsfälle können diese Blenden 36 auch
aus einem elektrisch leitenden Werkstoff bestehen, oder
alternierend angeordnet aus elektrisch leitendem und
nicht leitendem Material sein.
Die Durchflußöffnung 37 der Blenden 36 sind, bezogen
auf die Durchflußrichtung des Elektrolytes, die
entgegengesetzt zur Durchlaufrichtung des zu
beschichtenden Körpers 15 gerichtet ist, in ihrem
jeweiligen Querschnitt zwecks Verhinderung eines
Druckgefälles im Düsenkörper 34 stufenweise vergrößert.
Die kleinste Durchflußöffnung 37 befindet sich also in
der Ebene E, während die größte Durchflußöffnung 37
sich in der Ebene A befindet.
Wie Figur 4 weiter zeigt, weisen die Blenden 36 mehrere
drallerzeugende, zur Durchlaßöffnung 37 tangential
ausgerichtete Einschnitte 39 auf.FIG. 4 shows one of the
The flow opening 37 of the
As FIG. 4 further shows, the
Die Wirkungsweise der beschriebenen Vorrichtung ist wie
folgt:
Der zu beschichtende Körper 15 ist an einer nicht dargestellten
Stromquelle - beispielsweise über stromführende
Kontaktrollen - an ihrem Minuspol angeschlossen,
während der Düsenkörper 34 über Stromschienen 13 mit
dem Pluspol der nicht dargestellten Stromquelle verbunden
ist. Die Stromdichte wird über an sich bekannte
Schaltungselemente entsprechend dem durchzuführenden
Verfahren auf 10 bis 400 A/dm2 eingeregelt. The operation of the described device is as follows:
The
Die dem zu beschichtenden Körper 15 aufgeprägte
Eigengeschwindigkeit wirkt in der Durchlaufrichtung.
Das zwischen dem Hohlkörper 30 und dem Düsenkörper 34
unter Druck stehende Elektrolyt 18 tritt durch die Bohrungen
44 des Düsenkörpers 34 hindurch.
Das über die Pumpe 16 bewegte Elektrolyt 18 wird beim
Durchfließen der Bohrungen 44, da diese als Lavaldüsen
wirken, beschleunigt und in einem Winkel α schräg zur
und entgegen der Durchlaufrichtung des zu beschichtenden
Körpers 15 sowie unter dem Drallwinkel β eingespritzt.
Durch die gleichmäßige Anordnung der Bohrungen
44 im Düsenkörper 34 ist ein gleichmäßiges Auftreffen
des Elektrolytes 18 auf die gesamte Oberfläche des zu
beschichtenden, sich entgegen der Strömungsrichtung
bewegenden Körpers 15 gewährleistet.
Hierbei addieren sich die entgegengesetzt gerichteten
Bewegungsvektoren des Körpers 15 und des eingespritzten
Elektrolytes 18 und bewirken unter der Strahlwirkung
der Bohrungen 44 an der Oberfläche des zu beschichtenden
Körpers 15 eine über die gesamte Oberfläche wirkende
turbulente Umströmung. Diese turbulente Umströmung
zerstört die bei der Galvanisierung entstehende
Diffusionsschicht praktisch vollständig.
Durch die zwischen den jeweiligen Bereichsebenen 11 der
Bohrungen 44 angeordneten Blenden 36 mit ihren gestuften
Durchlaßöffnungen 37 wird der Druck des Elektrolytes
18 im Düsenkörper 34 über dessen gesamte Länge konstant
gehalten. Gleichzeitig wirken diese Blenden als
örtlich begrenzte Stromschnellen für das Elektrolyt 18,
so daß vom Galvanisierungsprozeß her gesehen, ein auf
den Körper 15 pulsierend wirkender Stromfluß erzeugt
wird.The natural speed impressed on the
The
Here, the oppositely directed movement vectors of the
By means of the
Durch diese Maßnahmen können Stromdichten zwischen
Elektrolyt 18 und Oberfläche des zu beschichtenden
Körpers 15, am Beispiel einer galvanischen Verzinkung,
von 10 bis 400 A/dm2 gewählt werden. Auf diese Weise
kann der galvanische Beschichtungsvorgang beschleunigt
im Vergleich zu den bisher bekannten Verfahren und
können wesentlich dickere Schichten pro Zeiteinheit
aufgetragen werden als dies bislang möglich war.These measures allow current densities between 10 and 400 A / dm 2 to be selected between
Der Führungsring 26 hat die Aufgabe, einen Kurzschluß
zwischen Körper 15 und Düsenkörper 34 zu verhindern,
der dann zustande kommen würde, wenn der Körper 15
aufgrund der Relativbewegungen zwischen Körper 15 und
Elektrolyt 18 und den dadurch hervorgerufenen
Schwingungen den Düsenkörper 34 berühren würde.The
Selbstverständlich ist es je nach Qualitätsanforderung,
verwendeter Werkstoff oder Legierungsart möglich, mehr
oder weniger Bereichsebenen 11 zu verwenden, als in
diesem Ausführungsbeispiel beschrieben.Of course, depending on the quality requirements,
used material or type of alloy possible, more
or use
Claims (12)
- Galvanic process for galvanic or chemical treatment, particularly for the continuous application of metallic coatings to a body conveyed in the direction opposite to the flow of an electrolyte which is passing through a hollow body and which has an addition of metal ions and which is connected to the negative pole of a current source in order to act as a cathode, while the hollow body is connected with the positive pole of the current source, in order to act as an anode, the flow speed of the electrolyte, which said speed can be influenced by a pump, and the speed of motion of the body to be coated being selected to ensure that a turbulent flow occurs on the surface of the said body to be coated, characterised by the operation of spraying the electrolyte (18) onto the periphery of the body (15) from all sides at angles (α , β) oblique to and in opposition to the direction in which the body (15) passes and by stepwise partial alteration of the flow speed of the sprayed electrolyte (18) in relation to the body (15), for the purpose of completely dissolving the diffusion coating on the entire surface of the body (15) to be coated, and by the regulation of the current of the source in such a way that a current density of 10 to 400 A/dm2 prevails on the surface of the body (15).
- Apparatus for the performance of the process according to Claim 1, characterised by the fact that for the treatment of the body (15) a hollow body (34) is provided which acts as a nozzle body and which is positioned centrally in a hollow body (30) through which electrolyte (18) flows, the nozzle body (34) having a number of radial borings (44) acting as nozzles and positioned in a number of cross section zones (11) which are spaced apart and which are inclined both with respect to the longitudinal axis (16) of the nozzle body and with respect to the relevant cross section zone (11) by angles (α) and (β), the nozzle body (34) being provided with screens (36) which are situated in the through-flow passage (35) and which surround the body (15) to be treated and which are situated in planes (A,B,C,D and E) between the outlet apertures of the borings (44) and of which the through-flow passages (37) increase stepwise in cross section in the direction opposite to the through flow (5) of the body (15) in order to prevent a pressure gradient from occurring in the nozzle body (34).
- Apparatus according to Claim 2, characterised by the fact that the nozzle body (34) is coated on all sides and that the inner lateral surface of the hollow body (30) is coated on the end surfaces (31,32) with an insoluble metallic layer (38) of a metal of the platinum group and of which the layer thickness amounts to between 2 and 20 µm.
- Apparatus according to Claim 2, characterised by the fact that the screens (36) consist of an electrically non-conductive material.
- Apparatus according to Claim 2, characterised by the fact that the screens (36) consist of an electrically conductive material.
- Apparatus according to Claim 2, characterised by the fact that the screens (36) consist of an electrically conductive and electrically non-conductive material arranged in alternation.
- Apparatus according to Claim 2, characterised by the fact that the screens (36) have incisions (39) which generate twist and which are positioned tangentially to the through-flow passage (37).
- Apparatus according to Claim 2, characterised by the fact that a guide ring (26) of an electrically non-conductive material is provided at an outlet aperture (25) of the nozzle body (34) through which the body (15) to be coated leaves the nozzle body (34).
- Apparatus according to Claim 2, characterised by the fact that a pipe connection (24) for feeding in the electrolyte is axially offset through the longitudinal axis (41) by a distance (a) in relation to the transverse axis (40) of the apparatus (14).
- Apparatus according to Claim 2, characterised by the fact that the hollow body (30) surrounding the nozzle body (34) is positioned in a working container (12) through which the electrolyte (18) flows.
- Apparatus according to Claims 2 to 10, characterised by the fact that any desired number of hollow bodies (30) according to Claims 2 to 8 are connected in succession to one another in the working container (12).
- Apparatus according to Claims 2 to 11, characterised by use for the galvanic and chemical treatment of metallic and non-metallic surfaces.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4430652 | 1994-08-29 | ||
| DE4430652A DE4430652C2 (en) | 1994-08-29 | 1994-08-29 | Galvanic method and device for carrying out the method and its use for galvanic or chemical treatment, in particular for the continuous application of metallic layers to a body |
| US08/520,071 US5595640A (en) | 1994-08-29 | 1995-08-28 | Method and apparatus for continuous galvanic application of metallic layers on a body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0699781A1 EP0699781A1 (en) | 1996-03-06 |
| EP0699781B1 true EP0699781B1 (en) | 1998-05-27 |
Family
ID=25939634
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP95112519A Expired - Lifetime EP0699781B1 (en) | 1994-08-29 | 1995-08-09 | Electrolytic process for treating, particularly continuously plating a substrate |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US5595640A (en) |
| EP (1) | EP0699781B1 (en) |
| CA (1) | CA2156644C (en) |
| DE (2) | DE4430652C2 (en) |
| ES (1) | ES2119277T3 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030236489A1 (en) * | 2002-06-21 | 2003-12-25 | Baxter International, Inc. | Method and apparatus for closed-loop flow control system |
| US7273537B2 (en) * | 2002-09-12 | 2007-09-25 | Teck Cominco Metals, Ltd. | Method of production of metal particles through electrolysis |
| DE102006060255B4 (en) * | 2006-12-14 | 2012-09-27 | Jochen Holder | Process for the galvanic coating of workpieces in a zinc-containing electrolyte bath |
| JP5789723B2 (en) * | 2011-11-15 | 2015-10-07 | ポスコ | Horizontal electroforming apparatus for manufacturing high-speed metal foil and manufacturing method |
| EP2746432A1 (en) * | 2012-12-20 | 2014-06-25 | Atotech Deutschland GmbH | Device for vertical galvanic metal deposition on a substrate |
| US20150014176A1 (en) * | 2013-07-09 | 2015-01-15 | Raymon F. Thompson | Wafer processing apparatus having scroll pump |
| EP2910669B1 (en) * | 2014-01-30 | 2019-06-19 | Harry Igor Schaaf | Galvanic coating system and method for operating the same |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL235329A (en) * | 1958-01-22 | |||
| DE2151618C3 (en) * | 1971-10-16 | 1975-05-28 | Maschinenfabrik Augsburg-Nuernberg Ag, 8000 Muenchen | Method and device for the cathodic treatment of thin, electrically conductive fiber strands or bundles |
| US3894924A (en) * | 1972-11-08 | 1975-07-15 | Raytheon Co | Apparatus for plating elongated bodies |
| US3975242A (en) * | 1972-11-28 | 1976-08-17 | Nippon Steel Corporation | Horizontal rectilinear type metal-electroplating method |
| US3994786A (en) * | 1975-06-13 | 1976-11-30 | Gte Sylvania Incorporated | Electroplating device and method |
| US4409071A (en) * | 1982-12-27 | 1983-10-11 | International Business Machines Corporation | Masking for selective electroplating jet method |
| DE3317970A1 (en) * | 1983-05-13 | 1984-11-15 | Schering AG, 1000 Berlin und 4709 Bergkamen | DEVICE AND METHOD FOR GALVANIC DEPOSITION OF METALS |
| KR890001111B1 (en) * | 1983-09-07 | 1989-04-24 | 미쯔비시주우고오교오 가부시기가이샤 | Continuous alloy electroplating method and apparatus |
| DE3439750A1 (en) * | 1984-10-31 | 1986-04-30 | Inovan-Stroebe GmbH & Co KG, 7534 Birkenfeld | GALVANIZING PROCESS |
| SE469267B (en) * | 1991-07-01 | 1993-06-14 | Candor Sweden Ab | Surface treatment device, whereby a medium under pressure is aimed at a continuous material web in a cavity |
-
1994
- 1994-08-29 DE DE4430652A patent/DE4430652C2/en not_active Expired - Fee Related
-
1995
- 1995-08-09 EP EP95112519A patent/EP0699781B1/en not_active Expired - Lifetime
- 1995-08-09 DE DE59502321T patent/DE59502321D1/en not_active Expired - Lifetime
- 1995-08-09 ES ES95112519T patent/ES2119277T3/en not_active Expired - Lifetime
- 1995-08-22 CA CA002156644A patent/CA2156644C/en not_active Expired - Fee Related
- 1995-08-28 US US08/520,071 patent/US5595640A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| DE4430652A1 (en) | 1996-03-14 |
| CA2156644C (en) | 2004-12-14 |
| ES2119277T3 (en) | 1998-10-01 |
| DE4430652C2 (en) | 1997-01-30 |
| DE59502321D1 (en) | 1998-07-02 |
| US5595640A (en) | 1997-01-21 |
| CA2156644A1 (en) | 1996-03-01 |
| EP0699781A1 (en) | 1996-03-06 |
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