WO2010133222A2

WO2010133222A2 - Method and device for controlling electrochemical surface processes

Info

Publication number: WO2010133222A2
Application number: PCT/DE2010/000594
Authority: WO
Inventors: Egon Hübel
Original assignee: Huebel Egon
Priority date: 2009-05-22
Filing date: 2010-05-18
Publication date: 2010-11-25
Also published as: EP2432921A2; JP2012527525A; KR20120026487A; WO2010133222A3; DE102009023768A1; CN102439202A

Abstract

The invention relates to a method and a device for the electrochemical treatment of substrates in continuous installations or dip coating installations including the electric contacting of the material (1) on opposite edges by means of right-hand and left-hand contacts (3', 3''). According to the prior art, the material is treated to a different degree at a right angle to the direction of transport with the minimum being in the region of the center of the material. In order to achieve a completely even electroplating of the material, two electrolytic cells (8, 8'') which are preferably of the same size and have individual anodes (7', 7'') and rectifiers (6, 6'') are arranged at a right angle to the direction of transport as the right-hand and left-hand elements. The right-hand cell (8') is cathodically supplied with electroplating current via the left-hand contact (3'') and the left-hand cell (8'') via the right-hand contact (3'). The treatment of the material (1) can be controlled in a very precise manner, i.e. to give an even result, by differently set currents in the two cells (8', 8'') which currents act on the respective sides alternately in time, i.e. by simply controlling or regulating the current intensity of the rectifier (6', 6'') of the two sides.

Description

Method and device for controlling electrochemical

surface processes

description

The invention relates to the electrochemical treatment of electrically conductive base layers on level material. This preferably relates to plate-shaped or band-shaped substrates. The invention is suitable for electroplating or etching of printed circuit boards and conductor foils or other plates in continuous systems or Tauchbadanlagen. Furthermore, for strips of metal or metallized plastic films in roll-to-roll systems. It should be deposited using the largest possible current density, a uniformly thick metallic layer on the entire large surface of the material, even if the initial metallized base layers are thin or very thin and therefore high impedance. Electroplating can take place on only one surface side or on both surface sides of the flat material. In all cases, the good may be sections as sheets and plates or endless from roll to roll. There are already proven technical solutions for this. The object of the invention is to control the electrochemical process so that a uniform electrochemical treatment of the same transversely to the transport direction and in Tauchbadanlagen a uniform treatment takes place without constructive adjustments of the plant to the material to be treated. In particular, when the electric current is supplied from the edges of the center region of the material, there should be no layered valley during plating or no layer thickness during etching. The object is achieved by the method according to claim 1 and by the device according to claim 7. The dependent claims describe advantageous embodiments of the invention.

Throughput plants and plants that produce the goods from roll to roll are preferably used for the production of mass products because of their low plant flexibility. These products are usually small printed circuit boards or conductor foils for z. B. BGAs (Ball Grid Arrays), RFIDs (Radio Frequency Identification), MP3 players, memory sticks, mobile phones, assemblies for PCs and like. They are arranged for a great benefit, which is referred to in this specification as a printed circuit board or generally as a good. The increasing miniaturization of electronics requires technically sophisticated fine conductor technology. This supports the invention by the planar plating of the required thin base layers of the material.

The material to be treated according to the invention is a global plate, printed circuit board or conductor foil. These become increasingly larger in practice. They have a usable area for the small goods and an unusable edge area with contact tracks thereon. The useful area should be treated electrochemically even with very large plates or surfaces with very good coating thickness distribution.

On each of the many arranged along the transport path of the conveyor system contact rollers or contact wheels, which may be at the same time transport rollers or transport wheels, located on both sides in the edge region depending on a rotating electrical contact. On both sides also transporting and contacting clamp contacts or sliding contacts can be arranged.

The material is fed via the two contact traces or contact areas at the edges with the cathodic current required for electroplating. The measures according to the invention for avoiding a valley of the layer thickness in the middle of the goods see transversely to the transport direction divided into two parts and electrically isolated anodes and their respective associated electrolytic cells, which are fed by at least one individually adjustable in the current rectifier with Galvanisierstrom.

Below are the transversely divided to the transport direction anodes or electrodes and the associated electrolytic cells and the contacts on the edge of the goods and the rectifier with the addition of right and left are called. In the edge region of the goods under the right anode and on the right-hand electrolytic cell is correspondingly the right-hand electrical contact or the right-hand contacts. Under the left anode and on the left electrolytic cell is accordingly the left electrical contact or the left contacts. The right anode is powered by at least one right rectifier with treatment current. The rectifier or rectifiers, together with the right-hand anode and the lower right-hand half of the material underneath, form the right-hand electrolytic cell. The left anode is powered by at least one left rectifier with treatment current. The rectifier or rectifiers together with the left anode and the lower left part of the goods underneath form the left one electrolytic cell. The surface of the material in each case forms the cathodic counter electrode during galvanization or the anodic counter electrode during etching. The same applies to the underside of the goods with the optionally there mirror image arranged electrolytic cells. The anodes or electrodes which are also divided there and the two half surfaces of the product to be plated, as the cathode or counterelectrode, also form right and left electrolytic cells, which are each fed with treatment current by at least one rectifier. According to the invention, the electrical galvanizing circuit of the right or the right rectifier is closed via the right anode and the right electrolytic cell and the right half of the cathodic material and thence through the base layer of the left half of the product via the left electrical contact. Accordingly, the electric galvanizing circuit of the left or left rectifier is closed via the left anode and the left electrolytic cell and the left half of the cathodic material and thence through the base layer of the right half of the material via the right electrical contact.

The left half of the product with the base layer thereon thus serves as an electrical conductor for the cathodic galvanizing of the right electrolytic cell. The right half of the goods with the base layer thereon serves accordingly as an electrical conductor for the cathodic Galvanisierstrom the left elektrolyti- see cell. Because of the very large distance of the contact means at the two edges of the goods, which are each far away from the associated electrolytic cells, which feed them with galvanizing, they are metallized less intense with advantageous side effect, as in an electrolytic cell according to the prior art. The rectifier or rectifiers on one side of the material in the region of a plant position or anode position form a rectifier pair with the rectifier or rectifiers on the other side of the material of a plant position or anode position. Each anode must be assigned at least one rectifier or more, correspondingly smaller sized rectifier. These bath power sources can z. B. also be associated with each individual cathodic contact of each page. In particular, at good, seen in the transport direction is long, z. B. 610 mm, only a few contacts in this direction are needed. In this case, each contact an individual rectifier can be assigned, whereby the contact current and superordinate the anode current is precisely controlled. In this case, all rectifiers associated with one anode are connected in parallel via the electrically conductive cathodic good. To simplify the following Description and figures, it is predominantly assumed that each electrolytic cell is associated with only one rectifier.

To explain the invention, two limit cases are to be considered first: The first limiting case exists when only one of the two rectifiers is switched on for the duration t. Along the continuous system at the usually multiple anode positions, the rectifier on one side is preferably switched on alternately with the rectifiers on the other side of the material. The duty cycle 1 1 of the rectifier of one side and the duty cycle 1 2 of the rectifier of the other side are preferably the same size. The second limiting case consists in rectifiers of a rectifier pair switched on at the same time with the same magnitude of current at one or more anode positions.

In the first limiting case, the left rectifier is initially switched off for the duration t. The right rectifier feeds the right electrolytic cell. This is done by the left base layer of the goods, the feeding of the galvanizing to the right cell. For this cell, this means that the current is fed into the base layer in the middle of the product. In this right cell, the electrical voltage drop in the base layer then increases from the center towards the right edge. Thus, the locally effective cell voltages as well as the local current densities decrease towards the right edge. This means an inclined plane on the right half of the material, wherein the mountain of the deposited layer, seen transversely to the transport direction, is in the middle of the material, although the material was contacted electrically at the edge, namely at the edge, which does not the right electrolytic cell is located. The same situation then applies to the left electrolytic cell where the right rectifier is off for the same period of time t. This results in an inclined plane on the left half of the estate, with the mountain again in the middle of the estate.

The galvanic deposition on the two halves of the material takes place in this example, successively and transversely to the transport direction exactly symmetrical, the valleys occur at the edges, over which the current was fed crosswise. In contrast, according to the prior art, the mountains of the inclined planes always occur at the edges. If at the same time the right and left rectifiers are switched on with the same amount of current in the second limiting case, then there is a complete symmetry of the currents and voltage drops. From both edges of exactly the same amount of electricity flows to the estate. In In this case, the respective electrical conductor in the base layer or the symmetrical voltage drop occurring there affects such that a valley of the deposited layer occurs exactly in the middle of the material.

The inventively controllable electrochemical treatment of the material takes place within these two limiting cases. By controlling or regulating the right and left galvanizing currents alternately and in different sizes, the layer thickness distribution can be set very precisely, i. H. flatten. With the difference of alternately on the right and left sides of different sized galvanizing the center region of the material can be galvanized even or exaggerated, although there are no contacts.

Thus, without conversion of the system to the different parameters of the products to be plated by means of the rectifier control technology can be reacted, in particular on different thin base layers, the transport speed, the thickness of the layer to be plated and the size of the average current density. The

Dimensions of the goods can be seen in the transport direction, apart from a minimum length, be arbitrarily long. With different dimensions of the goods, viewed transversely to the transport direction, appropriately adapted contact means are to be used. At the contact means are also in the distance of the tracks adjustable arranged contacts applicable.

When galvanizing in the continuous system, the layer thickness of the original base layer increases continuously. This also increases the electrical conductivity. This may require adaptation, ie the reduction of the measures according to the invention along the continuous system. When etching this is the reverse case. During this treatment, the thinning base layer becomes more highly resistive. This requires the measures according to the invention especially towards the end of the etching. In an etching process, the well-known puddle effect is to be considered at least on the upper side of the material. Due to this, the middle region of the material is etched less than the edge regions. For this purpose, the invention also proves to be very advantageous, especially when a combination of chemical and electrochemical etching is used. This can be done simultaneously or sequentially in the continuous flow system. For a uniform etching is achieved over the entire surface of the goods. Some electrolytes used have corrosive properties with respect to the base layer or starter layer. For very thin base layers such. B. sputter layers can then start a stop galvanization to protect them with both sides on the edges of equal currents. After this protective treatment in a short time, z. B. in 20 seconds, the galvanization of the goods can be continued with the method according to the invention.

The description of the invention is given by examples of galvanizing. Electrochemical etching reverses the described polarities of the electrodes and the rectifier. The resources of the right and across the estate opposite left side are hereinafter also referred to as feed pair. In dip baths, as in continuous flow systems, an inventive feed pair can be arranged. Preferably, in Tauchbadanlagen a second feed pair is used, which is transversely across the Good extending axis offset by 90 ° to the axis of the first feed pair.

The inventive electrochemical treatment of the material in a dip bath plant is particularly suitable if it is a large format plate such. B. a Fiat panel display or a film with preferably the same dimensions of a large production lot. A two-sided contacting at the opposite edges of the goods corresponds to the situation described in a continuous system. Accordingly, divided anodes with individual rectifiers are preferably to be used in the middle of the transport path. If it is possible to make electrical contact on all four edges, then advantageously four anodes with individual rectifiers are also to be used. This can be very large plates with a z. B. very thin sputtered layer can be galvanized as a base layer over the entire surface with a very uniform coating thickness distribution in a dip. To avoid the direct deposition mapping of the split anodes on the estate, a goods movement running in the plane of the goods can be used. In both feed cases, the leveling of the deposited layer by means of current control of the rectifier is carried out as described in detail using the continuous flow system.

The invention will be described below with reference to the schematic and not to scale figures 1 to 5 on. Figure 1 shows in cross-section of a continuous system, the basic arrangement of the modules or construction elements according to the invention.

FIG. 2 shows a plan view of the basic arrangement of a plurality of assemblies or construction elements according to the invention. FIG. 3 shows the electrical equivalent circuit diagram of the arrangement according to the invention.

FIG. 4 shows measurement results which were determined on a resistance model of an electrolytic cell and a cell voltage / current density characteristic of a copper bath based on sulfuric acid.

FIG. 5 shows, in a simplified illustration, transversely to the transport direction, the courses of the electrodeposited layers or layer thickness distributions on the product in the case of alternately large galvanizing currents in the electrolytic cells.

In FIG. 1, the flat material 1 to be electrolytically treated is located between rotationally driven contact means 2. It is to be galvanized both on the upper side and on the lower side. The estate 1, z. As plates are transported along the transport path through the electrolytic cells arranged there. This is done here perpendicular to the plane of the drawing. The contact means 2, which are shown here as a roller, can also be means of transport for the good. The contact means 2 may also be rotating shafts with contact wheels and the like, as well as non-rotating shafts with sliding contacts. On the two sides of the transport track are on the

Contact means 2 electrically conductive contacts 3 as z. As discs, rings, segmented discs, wheels or brushes, each at least partially made of metal arranged. The arrangement according to the invention is preferably divided symmetrically into a right side R and into a left side L transversely to the transport direction. In this description of the invention, the reference numerals of the right sides and the right arranged design elements with a simple high stroke, z. B. 3 ', and the left arranged construction elements with double high strokes, z. The axial distance of the two contacts 3 'and 3 "on the contact means 2 determines the width of the material 1 to be produced transversely to the transport direction. The useful area is smaller by the width of the contact tracks on the right and left edges of the goods. The supply of Galvanisierstromes to the contacts 3 ', 3 ", which are located in the work container, not shown, the continuous system and in the electrolyte 14, via electrically conductive stub shaft 4', 4". To transmit the current to the rotationally driven contact means 2 and thus to the stub shafts serve sliding contacts 5 ', 5 "or rotary contacts, which are arranged outside the electrolyte., Rotary contacts can advantageously be made hermetically sealed .The sliding contacts or rotary contacts are connected by means of electrical conductors to the negative poles of the galvanizing current sources 6 \ 6". The positive poles of the galvanizing current sources are connected to soluble or insoluble anodes 7 ', 7 "According to the invention, there are two anodes 7' and 7" transversely to the transport direction, which preferably extend to the middle of the transport path. In the direction of transport, these individual anodes 7 ', 7 "can extend over a length of, for example, one meter or more. For individual rectifiers per contact 3', 3", these anodes can also extend over the entire length of the continuous system. In particular, with a short system in the transport direction, it may also be sufficient to install only one rectifier per side. The dimensions of the anodes and the number of rectifiers are determined from a design point of view. The rectifier or galvanizing current sources 6 ', 6 "may be DC sources as well as unipolar or bipolar pulse current sources. In this description, in the case of bipolar pulse current sources having the indicated polarity, the predominantly acting polarity is meant.

The anodes 7 'and 7 "or electrodes together with the corresponding cathodic surface of the material 1 form electrolytic cells 8' and 8". This surface is the cathodic base layer 9 to be electroplated or the counterelectrode, which is usually located at the top and at the bottom of the product 1. Correspondingly, electrolytic cells 8 ', 8 "must also be located at the top and at the bottom of the transport path, these being shown in Figure 1, resulting in a mirror-image arrangement The invention will now be described by way of example only by the example of electroplating the top. The descriptions also apply to the underside of the product 1, even if there is a base layer 9 which is to be galvanized or electrochemically etched, The invention is also suitable for the electrolytic reinforcement of large areas and plated-through holes.

The electroplating current of the right electrolytic cell 8 'generated by the right electroplating current source 6' passes through the left sliding contact 5 ", the left shaft stub 4", the left contact 3 "and the left half of the base layer 9 of the material to the right Thus, with the left plating current source (s) 6 ", the right electrolytic cell 8 'is fed with the plating current from the left side, ie from the center of the transport path. This means that due to the electric voltage drop in the base layer 9 of the right side Layer thickness course arises, which has the maximum transverse to the transport direction in the middle of the goods. The minimum occurs on the right edge of the material 1 in the vicinity of the local contact path. The electrical voltage drop, which occurs in the left-hand base layer 9, has no influence on the right electrolytic cell 8 'and the voltage drop occurring therein in the base layer 9 when the left electroplating current source 6 is switched off. However, the left half of the base layer 9 acts as an electrical conductor For the galvanizing current flowing to the right cell 8 ', only the terminal voltage of the preferably current-controlled right galvanizing current source (s) 6', for example by 0.6 volts, adjusts itself to this voltage drop left electrolytic cell 8 "as a cell voltage. It is so small that metal deposition on the surface of the material does not occur in this area.

When the right galvanizing current source (s) 6 'is switched off and the left galvanizing current source (s) 6 "are switched on for the same period of time, the left half of the product is galvanized as described above, in which case the maximum of deposition occurs in the middle of the product on the left edge.

In this sequential electroplating of the two halves occurs in the sum again an unwanted uneven deposition on. This unevenness is already somewhat smaller than in the feeding of the galvanizing current from the two edges according to the prior art. However, in the arrangement according to the invention, the maximum occurs very advantageously in the middle of the material 1, although there are no contacts here. The correction of this uneven layer thickness distribution can be carried out in a simple manner using the three methods described below:

The inclined planes of the layer thicknesses with the maximum or mountain in the middle of the material can be compensated in the continuous system with further, arranged in the transport direction electrolytic cells according to the prior art with undivided anodes. In these cells, the inclined planes run on the material 1 in the opposite direction, ie the mountain occurs at the edges, whereby the elevations according to the invention in the middle can be compensated. However, this balance is only suitable for a small product range. Thereupon, the number of electrolytic cells along the transport path in the respective embodiment must be coordinated. In practice, however, there are a wide variety of goods to be galvanized. So z. B. thinnest base layers to be provided with a thin or with a very thick electroplating. A thicker base layer can also be galvanized with a thin or with a very thick electroplating layer. In these cases are very different constructive corrective measures required. There is much to correct in one case, and little is to be corrected, especially with a thicker base layer, because here the oblique planes have small slopes due to the lower voltage drops in the base layer. A continuous flow system, equipped with this invariable measure for the correction of the inclined planes, can therefore only cover a limited range of parameters of the goods.

The flexibility of the continuous system according to the invention with respect to the parameters of the material increases when the above limit of the correction in the transport direction is adjusted as needed. This is done according to the invention z. For example, by means of electrical switching means 13, which can connect the right and left anodes 7 ', 7 "in each anode position AP of the continuous system along the transport path, as required, in this case, the boundary of the course of the inclined planes from the center of the Good to the edge and vice versa without plant conversion, changed only by a control of the switching means 13 and thus adapted to the needs given by the good Thus, for example, 12 anode positions AP of a continuous system in the transport direction at the last 5 anode positions, the right and In this case, the respective right and left galvanizing current sources 6 ', 6 "are connected in parallel because the electrically conductive material also electrically connects the cathodic contacts to each other , This allows the directions of the gradients of the inclined planes in each anode position to be controlled. It is practically a stepwise control. The effect or reduction of the stage can be achieved in that instead of the low-resistance switching contact 13, the electrical connection by means of a resistor in series with the switching contacts 13 takes place. Each anode position represents a treatment stage. The same applies to the first anode positions AP of a continuous system, which can be electrically connected to each other by means of the controlled circuit, if necessary.

The feeds of the electroplating stream according to the invention for attaining inclined planes with the mountain in the middle on the one hand can be arranged alternately successively along the transport path for layer thickness correction even with feeds in electrically connected anodes to achieve inclined planes with the valley in the middle.

In the switched electrical connection of the anodes 7 'and 7 "by the switching means 13, the individual Galvanisierstromquellen 6', 6" on the right and left By means of the individual plating current sources 6 ', 6 ", the currents on the two sides are reduced as a result of the current-controlled plating current sources 6', 6" according to their nominal values In this case too, the at least two rectifiers 6 ', 6 "per anode position prove to be an advantage. In contrast, the currents are distributed differently in an undivided anode according to the prior art and a single galvanizing current source, which supplies the goods with power on the right and left. The cause is there, among other things, not the same size electrical contact resistance on both sides of the goods.

However, the invention also allows a stepless and very flexible design for the controlled achievement of a flat layer thickness distribution over the entire good, which may have any parameters with respect to the galvanization to be carried out. In this method of electrochemical treatment, it is advantageous not to set the two limiting cases successively along the transport path in the continuous system in the subcells, but to average them between the limiting cases. The current intensities of the right and left galvanizing current sources are set to be different, depending on the anode position in the transport direction of the product or else alternately within the anode positions, or within a number of contacts with individual rectifiers. This makes it possible to deposit a nearly flat layer in the electrolytic subcell with the larger current. With increasing difference of these currents, an inclined plane is formed with the mountain in the middle of the material in the electrolytic subcell, which carries the larger current. The same happens then on the other side of the goods in the local electrolytic subcell of the same feed pair.

Conversely, an increasing inclined plane is deposited with a mountain at the edge of the material when the electrolytic currents of the two sides or partial cells are approximated. With current equality in the electrolytic sub-cells, d. H. in the left subcell and in the right subcell again the same size mountains of the layer occur at the two edges of the property.

These control options according to the invention result in the sum of a flat layer across the estate, which is the goal in electroplating technically demanding goods. Since all galvanizing current sources can be set individually in terms of amperage, all electroplating or electrochemical treatment can be performed on all precom- menden parameters of the goods for level deposition individually adjusted very precisely.

In all cases, a planar layer thickness distribution is achievable solely by controlling the alternately different galvanizing currents of the right and left rectifiers 6 ', 6 ".An the designations 6' and 6" are in each case one

To understand rectifier or more correspondingly smaller sized rectifier. These smaller rectifiers are electrically connected in parallel via the material and via the associated anode. FIG. 2 shows an arrangement according to the invention in plan view. Shown are 5 anode positions APl to AP5 respectively with right and left anodes 7 ', 7 "The length of the anodes in the transport direction can be up to one meter and more in design direction, especially in short continuous flow systems, the anodes 7', 7" also over extend the entire length of the plant. 2, only one contact means 2 and one rectifier are shown in the region of the anodes 7 ', 7. In the case of particularly long anodes, seen in the transport direction, a corresponding number of contact means 2 per anode position and one or more rectifiers are arranged in practice. In the case of several contact means 2 in the region of an anode position in the transport direction and only one electroplating current source per side and anode position, the contacts 3 ', 3 "of these contact means 2 are electrically connected to each other at least via the base layer of the product and / or via electrical conductors. The number of rectifiers 6 can also be increased to the extent that each contact means 2 is assigned an individual rectifier. In this case, each different size contact resistance can be compensated by the current-controlled rectifier. Are there, as shown in Figure 2, two contacts 3 ', 3 "on the rotating contact means 2, then there are two sliding contacts for power transmission or

For structural reasons and / or cost reasons, only one contact 3 ', 3 "can be arranged per contact means 2. Along the transport path, in this case the right and left contacts 3 ', 3 "are alternately distributed on the contact means 2. Because several contact means 2 always roll on a good as a section and contact it electrically, there is no disadvantageous influence on the method according to the invention. Only the size of the current to be transmitted by a contact is doubled.

The boundaries between the right and left anodes may be cut obliquely to make the transition from the right to the left in the deposited layer on the material to achieve stepless. Between the two anodes 7 ', 7 ", an electrical insulating wall 12 may be arranged to prevent a continuous mutual metallization and demetallization of the anodes.

The electroplating on the two sides alternately intensive according to the invention can take place from anode position to anode position. But it can also take place alternately in each anode position. To achieve a symmetry of deposition is preferably the treatment time 1 1 one side equal to the treatment time 1 2 the other side. The same applies to the size of the instantaneous currents of the rectifiers 6 ', 6 ", which are likewise to be set alternately with equal differences: In FIG. 2, the anodes 7 actually cover the contact means 2. For better clarity, the contact means in FIG 3 shows the electrical equivalent circuit diagram of the feed pair according to the invention at an anode position The distributed electrical base resistors 10 ', 10 "in the base layer extend just like the material from the right contact 3' to the left contact 3" Electrolytic cells are distributed bath resistors 11 ', 11 "are formed, which are formed by the electrolyte.

In the first limit case has an intellectually switched off Galvanisierstromquelle, z. The right electroplating current source 6 ', the still active electrolytic cell 8 "its feeding the cathodic Galvanisierstromes from the Galvanisierstromquelle 6" in the center of the arrangement, d. H. the transport path and thus also in the middle of the goods. The anode 7 ', which is connected to the switched off Galvanisierstromquelle 6', is inactive in this case. In the region of this inactive anode 7 'is not galvanized. Therefore, the electrical voltage drop in the base layer under this anode 7 'is also unaffected by the instantaneous plating in the electrolytic cell 8 ". The valley of the layer is at the edge of the material to which no current was fed.

The situation in the second limiting case, in which both galvanizing current sources 6 'and 6 "are set with the same current intensity, can also be seen, in which case equal currents flow from the right and left contacts 3', 3" into the base layer of the product. All voltage drops are symmetrical. As a result of the voltage drops in the base layer or in the base resistors 10 ', 10 ", the local cell voltages between the cathodes, ie the base layer and the anodes, decrease correspondingly symmetrically to the center This results in a decreasing current density from the edges towards the center with there correspondingly smaller deposit.The valley of the layer is here in the middle of the estate. In the geometric center, the base layer is as de-energized as in a bilateral feed of the material and with undivided anode according to the prior art. This symmetry shifts when the current intensities of the two galvanizing currents are set to different levels. Figure 4 shows the quantitative effects of the current differences ΔI in the left L and right R electrolytic cells 8 ', 8 "on the anode / cathode voltage corresponding to the cell voltage of an electrolytic cell, because an electrolytic cell filled with electrolyte and one inside The data were determined by means of a resistance model, which simulated a typical printed circuit board and an electrolytic cell almost realistically.The structure of the resistance model corresponds to the equivalent circuit of Figure 3. However, it was twice as large With the families of curves for the measuring points across the material on the X2 axis and the associated anode / cathode voltages on the Y2 axis, a cell voltage / current density characteristic of a real electrolytic cell of a sulfuric acid copper bath is plotted

Cell voltage Uz is on the Yl axis and the associated current densities i are plotted on the Xl axis. This Uz / i characteristic curve makes it possible to determine the real current densities i for the anode / cathode voltages measured in the resistance model, or the cell voltage Uz. The current density is in A / dm ² and the cell voltages are plotted in volts. The typical course of this Uz / i characteristic shows that at cell voltages Uz below 1.5 V almost no metal deposition can take place. The cathodic current density i is less than 0.2 A / dm ^{2 here} . However, it helps to prevent the return of metal from the surface of the material. In the range of the cell voltages Uz of 1.5 V to 2.5 V, the current density increases from 0.2 A / dm ² to 7.6 A / dm ² . The family of curves of the anode / cathode voltages shows that at currents in the left electrolytic cell, which are only up to 50% of the currents in the right electrolytic cell, anode / cathode voltages in the range of 1.5 V or less occur. With these small anode / cathode voltages or cell voltages, there is virtually no deposition. This is only galvanized in the right electrolytic cell. The course of the anode / cathode voltages or cell voltages can be adjusted so that a mountain or valley of the deposited layer occurs in the middle of the material. The largest mountain is at the left 0% and right 100% of the galvanizing. A valley arises in the middle of the estate at z. B. 70% left and 100% right of the galvanizing. At 100% plating current in both electrolytic subcells, the anode / cathode voltages are completely symmetrical. This occurs in the middle of the estate, the largest valley. It can be seen from the diagram that the valley is galvanized with a current density i of 4.6 A / dm ² and the mountains with current densities of 7.6 A / dm ² . The current density differences Δl thus amount to 3 A / dm ² in this example chosen. This corresponds to the prior art with a two-sided power supply. The anode / cathode voltage curve left 30% right 100% shows a nearly flat course in the right subcell. The difference Δ2 of the anode / cathode voltages is approximately 0.1 V. Accordingly, the current density difference in the right-hand electrolytic cell is approximately 0.6 A / dm ² . This means a virtually flat metallization on this half of the estate.

Then the current is mirrored, d. H. 100% on the left side and reduced power on the right side, eg. B. 30% set. The result is then an almost completely level deposition of the metal on the material transversely to the transport direction.

Also, the remaining in this example small current density difference, which occurs symmetrically on the two sides, can be inventively einbnen. For this purpose z. B. along the transport path to use at least one pair of anodes, which has approximately in the middle of one half of the anode division. Accordingly, at least one anode pair is arranged, which is divided in the middle of the other half. With adapted current differences ΔI of the respective two sides of these asymmetrical anode pairs, it is then also possible to prefer these regions in the coating, ie. H. be increased and thus leveled. Again, the controls of the invention can be used for deposition. The diagram of Figure 4 shows the situation of a continuous system transverse to the transport direction. In principle, it also applies to a dipping bath with stationary goods. In this immersion bath, a further 90 ° offset anode pair can be arranged with corresponding rectifiers per surface side. This creates an extended control option for the deposition of even layers on a large plate-shaped material. This is particularly advantageous when a single good fills the entire Galvanofenster.

FIG. 5 shows the qualitative profiles of the inclined planes transversely to the transport direction in the right and left regions of the transport path. Shown are the situations at different currents I and symbolically in percent, each after the Electroplating, ie after passing through the goods through the corresponding anode positions.

The sum of the deposits in the region of the two electrolytic cells 8 'and 8 ", which successively took place in the preferably equally long times 1 1 and 1 2, is shown by the profile shown in the figures below

Driving through the goods through the electrolytic cells of the anode positions involved. FIG. 5 a shows the limiting case with the right and left galvanizing currents, which were set with the same magnitude of current I and switched on at the same time. As a result, the valleys of the inclined planes are in the middle of the estate. The layer thickness differences are denoted by delta, which is maximum here.

FIG. 5 b shows the other limiting case in which only the right electroplating current source is switched on in the first anode position or for the first time 1 1 and only the left electroplating current source is switched on in the subsequent anode position or for the second time 1 2. In sum, the mountains of incline arise in the middle of the estate. Again, the delta is maximum. Overall, however, less metal was deposited with the same exposure time than in the limiting case of Figure 5 a. FIG. 5 c shows the situation between the two limiting cases with simultaneously switched on galvanizing current sources on the right and left side for the simultaneous supply of the right and left electrolytic cells, but alternately with different current intensities I. The differences of the current strengths I, to be recognized at the zero current line, are set so that the sum of the deposits gives a flat layer. The delta is zero here, which can be achieved according to the task. The leveling is shown here after two time periods, namely 1 1 and 1 2. These time periods can also be the treatment times corresponding to the transport speed of the material in an anode position for 1 1 and in the following anode position for 12. The times for 1 1 and 12 and the associated currents I can also be formed and adjusted over several anode positions with the respective anode lengths and the transport speed, whereby the leveling over several anode positions with the corresponding different currents I of the right and left Galvanisierstromquellen done.

FIG. 5 d shows an imperfect correction of the layer thicknesses in both halves of the product. However, this example shows that individual processes of the layer thickness distribution can be achieved with the method according to the invention solely by controlling the galvanizing currents I. The stated currents I in percent are only approximate values In practice, according to an initial experiment, there are empirical values for the current intensities of the galvanizing current sources to be set.

LIST OF REFERENCE NUMBERS

1 Good, plate, circuit board, foil, tape

2 contact means 3 contact

4 stub shaft

5 sliding contact, rotary contact

6 Rectifier, bath power source, galvanizing power source, etching power source

7 electrode, anode 8 electrolytic cell, subcell

9 base layer, counter electrode

10 base resistance

11 bath resistance

12 insulating wall 13 switching contact, switching means

14 electrolyte

15 transport direction arrow

AP anode position, electrode position R right

Left

Claims

claims

1. A process for the electrochemical treatment of good (1) in continuous systems, dip baths or belt systems from roll to roll with electrolytic cells (8) formed from soluble or insoluble electrodes (7) and the surface of the material to be treated as a counter electrode (9) an electrical contact (3) of the goods (1), seen across the estate, at opposite edges of the same by means of right and left or all-side contacts (3 ', 3 "), in particular for galvanizing or etching substrates such. B. printed circuit boards, conductor foils, metallized

Plastic films, metal foils or metallized glass panes, characterized in that at least two electrolytic cells as right and left cells (8 ', 8 ") with right and left electrodes (7', 7") and transverse to the transport direction or across the good with at least one adjustable rectifier right (6 ') and with at least one adjustable left rectifier (6' ') are formed as a feed pair, wherein the right electrolytic cell (8') via the one or the left contacts (3 ") is fed with treatment current and the left electrolytic cell (8 ") is fed with treatment current via the one or more right contacts (3 ').

2. The method according to claim 1, characterized in that the right and left electrolytic cells (8 ', 8 ") by the rectifier (6', 6") with different sized treatment currents right and left alternately in the same or nearly the same time periods ( t 1, 1 2) are fed.

3. The method according to any one of claims 1 to 2, characterized in that the temporary electrochemical treatment with a maximum intensity in the middle or in another region of the material transverse to the transport direction in combination with a temporary electrochemical treatment with a minimum of intensity in the middle or in the other region of the goods is compensated transversely to the transport direction such that in the sum, seen transversely to the transport direction, a uniform treatment.

4. The method according to any one of claims 1 to 3, characterized in that arranged transversely to the transport direction of the goods (1) through electrodes or with right and left electrodes (7 ', 7 "), which are electrically connected to each other, an electrochemical treatment takes place, which has a minimum in the middle of the goods.

5. The method according to any one of claims 1 to 4, characterized in that the alternating electrochemical treatment with different current levels in the right and left electrolytic cells (8 ', 8 ") both within an electrode position (AP) and after an electrode position or after several electrode positions, seen along the transport path takes place.

6. The method according to any one of claims 1 to 5, characterized in that in Tauchbadanlagen additionally fed a feed pair as the upper and lower pair, the treatment stream in the estate, the processes of the invention are carried out mutatis mutandis, as described for the right and left feed pair ,

7. Apparatus for the electrochemical treatment of good (1) in continuous systems, dip baths or belt systems from roll to roll with electrolytic cells (8) formed from soluble or insoluble electrodes (7) and the surface of the material to be treated as a counter electrode (9) an electrical contact (3) of the goods (1), seen across the good, at opposite edges thereof by means of right and left or all-side contacts (3 ', 3 "), for electroplating or etching of substrates such as printed circuit boards , Conductor foils, metallized plastic foils, metal foils or metallized glass panes, using the method according to claims 1 to 6, characterized in that two electrodes (7) are provided as right and left electrodes (7 ', transverse to the transport direction as feed pair

7 ") which are electrically insulated from each other and are supplied with treatment current by at least one right-hand adjustable rectifier (6 ') and at least one left adjustable rectifier (6"), the positive pole of the right-hand galvanizing current source (n) being plating. (6 ') at the right anode (7') and the negative pole of the right galvanizing current source (s) (6 ') at the far left

Edge of the product (1) is electrically connected via the at least one contact (3 ") located there, and that the positive pole of the left galvanizing current source (s) (6") at the left anode (7 ") and the negative pole of the left Galvanisierstromquel - le (n) (6 ") at the far right edge of the good (1) via the at least one contact (3 ') located there is or are electrically connected and that during electrochemical etching, the rectifier (6) and electrodes (7) reversed polarity are connected.

8. The device according to claim 7, characterized in that in the continuous system seen in the transport direction successively some or alternately several Electrode positions are arranged with right and left electrodes (7 ', 7 ") and, viewed transversely to the transport direction, continuous electrodes.

9. Device according to one of the claims 7 to 8, characterized in that switching means (13) are provided with or without series resistance, by means of which the right and left electrodes (7 ', 7 ") are electrically connected to each other as needed.

10. Device according to one of the claims 7 to 9, characterized in that in Tauchbadanlagen a second feed pair feeds the treatment stream in the estate whose Gut opposite feed points are arranged at about 90 ° to the feed points of the other feed pair.