JP2007503527A - Apparatus and / or method for depositing metal and / or metal alloy from metal organic electrolyte - Google Patents

Abstract

Apparatus for depositing metals or alloys from organometallic electrolytes, especially organometallic complex salts in organic solvents, on objects (7) comprises a coating section (3). This is connected to processing sections (2, 4) and has feed (20) and outlet (40) chambers for the products which prevent entry of oxygen and moisture. Siphon washers (60, 61) and partitions (53, 54) seal the coating section from the other sections and a hood (5) encloses them which maintains an inert gas atmosphere. An independent claim is included for a method for depositing metals or alloys from organometallic electrolytes, especially organometallic complex salts in organic solvents, on objects using the apparatus.

Description

  The present invention deposits a metal and / or metal alloy, particularly a metal organic complex salt in an organic solvent, from an organometallic electrolyte on a product, and at least one coating for coating the product, at least one additional treatment unit. And generally relates to an apparatus and method having at least one sluice chamber for carrying a product in and out of the apparatus through a water channel without penetration of oxygen and / or moisture.

  As is common in traditional galvano technology, electrodeposition of alloys from aluminum, magnesium and their aqueous systems is not possible due to the very low potential of these elements. Although there have been a number of approaches to the deposition of aluminum, magnesium and alloys from these non-aqueous systems over the past few decades, only deposition from aluminum alkyl or magnesium alkyl containing complexes has been successful on an industrial scale. Here, electrolyte variants with corresponding appropriate process control and analysis have had some success for most of the various applications. In some cases, large-scale industrial applications using these have become possible.

  As is well known, the alkyl metals used to produce each electrolyte variant react very vigorously with oxygen and water to form reaction products such as alkoxy compounds or aluminum oxanes. These reaction products can no longer form additional complexes with alkali metals or alkali halides used in the formulation of the electrolyte. It remains in the electrolyte as a soluble impurity and in this case reduces electrical conductivity. Similarly, the maximum usable current density increases with increasing concentrations of these reaction products, thereby losing the coating process step cost-effectively and in some cases also good quality.

  The above-mentioned series of problems were already studied in November 1987 at the Guorg Zion Ohm Technical Laboratory in Nuremberg. In order to guarantee the long service life of the electrolyte and the optimum layer quality, alkyl-based metal organic electrolysis Results have been obtained that oxygen and / or moisture penetration into the coating system in which the liquid is present should generally be avoided. Apart from the chemical or electrochemical defects due to oxygen and water penetration into the coating system, it is also reliable to avoid such oxygen and / or water penetration into the coating system. And safe operation, especially with regard to process reliability and manufacturing safety and with respect to the environment.

  Various state-of-the-art coating systems are well known, and some approaches to avoid oxygen and / or moisture penetration into each part of the coating system are included. In such systems, electrolytic coating of seamless metal or non-metallic products containing metals or alloys from aprotic electrolytes that do not contain water or oxygen is provided in a continuous process, and DE 197 16 493 C2. A rinsing and drying step is added for this purpose, which is intended to remove aqueous residue. In addition, it is provided to discharge the coated seamless product from the system through the sluice system. The sluice chamber contains a central chamber that contains the fill liquid and acts as a barrier to the air contained in the outer chamber. The third chamber contains an inert gas. In addition, a regeneration circuit is provided in which all the liquid used in the process is prepared, washed and recirculated.

  According to German Patent No. 30 23 827 C2, the outside is a sealed tubular cell, through which the material to be processed and in contact with the cathode moves particularly continuously along the anode in the axial direction Possible cells are well known. In order to prevent undesirable discharge of the electrolyte from the tubular cell and to prevent the penetration of air atmosphere into the cell, the tubular cell can be pressurized with a protective gas. According to this publication, a sluice structure consisting of several chambers is also provided, into which inert gas and / or inert liquid can be introduced to seal the chambers together.

  According to German Patent No. 199 32 524 C1, for the purpose of electrochemical treatment, in particular for the purpose of electrochemical coating of conductive or conductive parts, these parts can be filled with electrolyte solutions or treated. It is brought into a rotating basket which rotates in the middle and thus covers the entire part. The container is airtight. The processing of the parts in the basket takes place without any reintroduction. Each liquid or solution is simply pumped into the container once and again from there. The vessel is centrifuged each time for drying purposes, and the electrolyte solution residue is then centrifuged by pushing the basket. This system is not suitable for metal-organic electrolyte deposition because of its design.

  German Patent 41 18 416 A1 also discloses a device for coating parts, preferably relatively thin ones, in which the coating brings the parts into containers arranged adjacent to one another. Is done by. In that case, the container or the tank is in an inert gas atmosphere. In addition, a rinsing tank, an etching tank, and a sedimentation tank are provided. When various tanks are arranged in a common container, a sluice that is formed as a partition and through which a component to be processed can permeate is provided. For this purpose, this permeable partition is made of an elastic material in the infiltration region, rotates around an axis, moves together in such a way that a seal is formed, and in such a way that the seal is formed. It is formed by a pair of rollers that slide against the boundary wall.

  According to these above publications, the device will attempt to avoid all permeation of oxygen or moisture into the device in some areas of each device. For this purpose, only a part of the device is provided, for example, with a rinsing and drying device or a three-part sluice chamber.

  Thus, an object of the present invention is an apparatus and method for depositing metals and / or metal alloys from a metal organic electrolyte, which does not cause any safety-related problems, and that all of the solvent from the apparatus. It is to provide an apparatus and method which can almost completely avoid the exhaustion and in particular all reactions with oxygen and moisture from the ambient atmosphere of the electrolyte-based apparatus used.

  The object is to provide at least one device according to the preamble of claim 1 comprising a separation device for separation in connection with the gas of other parts of the device from the covering or for sealing these other parts against the covering. Realized by providing a siphon rinsing device and at least one hood component that can be filled with an inert gas and generally seals the covering, at least one siphon rinsing device and at least one additional covering. The The object with respect to the method according to the preamble of claim 17 is that the loading and unloading of the product through a substantially solvent-free channel is provided to the metal and / or metal alloy deposition device via at least one sluice chamber. The product is generally evacuated of gas and transferred to at least one coating, the product is coated with at least one coating, and the coated product has at least one siphon rinse device from the coating. Through which the gas is generally removed and transferred to the at least one output, and the finished product is transported through the water channel through at least one additional sluice chamber, where an inert gas atmosphere bell is connected to the device. This is realized by being held above all parts. The extensions of the invention are defined in the dependent claims.

  This provides an apparatus and method for depositing metals and / or metal alloys that can reduce the carryover of oxygen and water or moisture along with other impurities into the coating electrolyte as much as possible. Thereby, a long service life of the coating electrolyte can be guaranteed. The formation of undesirable reaction products, such as solvent effluent, can be suppressed very rapidly or almost completely prevented. Oxygen and moisture diffusion barriers are precisely provided between the various parts of the apparatus by providing a siphon rinsing device with a separating device that separates the gas atmosphere into the various parts of the apparatus and seals these parts of the apparatus together. The gas atmosphere in the generally sealed hood component surrounding each part of the device can be set to be optimal in each part of the device. As a result, it is possible to prevent all of the solvent from moving to the electrolyte region through the gas atmosphere. Since chemical incompatibility of the coating electrolyte with the cleaning solution or other solvent frequently occurs, it has been proved that there is a particular advantage in the separation of the gas atmosphere of each part of the apparatus itself. This allows safe and reliable operation. For one, by providing a generally hermetically sealed hood component, it is possible to enclose the entire atmosphere within the device and thereby separate it from the external atmosphere surrounding the device. This allows the evaporating solvent to be recovered before it is discharged from the apparatus and recycled to the corresponding part of the system. Thus, contamination of the ambient atmosphere around the apparatus can be generally eliminated. Second, it is possible to maintain a constant pressure in the hood component, but at the same time a pressure different from the pressure corresponding to the pressure in the ambient atmosphere. Preferably, a slight overpressure is maintained and monitored in at least some of the hood components as compared to the atmosphere surrounding the device. Preferably, at least one pressure maintenance device is provided which maintains a constant pressure in the hood component and / or a slight overpressure in the hood component compared to the external and / or ambient atmosphere. Thus, unintentional permeation of the external atmosphere into the device and thus contamination of the gas atmosphere within the device can thus be largely avoided.

  In order to be able to maintain a substantially constant pressure in the hood components, in particular in each hood part, and thus in particular slightly compared to the external atmosphere of the device, preferably at least one gas buffer is provided. , And each part, in particular the first and / or last part. Therefore, this type of gas buffering device is preferably provided at the inlet and outlet of the device, since pressure variations can occur due to loading and unloading of the product through the water channel. Gas shock absorbers are filled when an overpressure occurs outside the preselectable tolerance range in the hood component, and an underpressure outside the preselectable tolerance range occurs in the hood component. In some cases, for example, when the gas atmosphere is removed from each hood component to fill the sluice chamber with inert gas, it is emptied.

  Preferably, at least one oxygen monitoring device is provided in the at least one sluice chamber and / or part of the hood component. Preferably, at least one device for monitoring the solvent concentration is also provided in the sluice chamber. This makes it possible to continuously monitor the oxygen and / or solvent content in the gas atmosphere in each part of the apparatus. Since the sluice chamber serves to prevent the introduction of air or oxygen into the device, the oxygen content of the sluice chamber is determined by the introduction of the product through the water channel and the discharge of the air introduced with the product. And periodically monitored, for example, after rinsing the chamber with an inert gas. If the sluice chamber is open to the hood component, the oxygen content in the chamber should be as close to zero as possible so that oxygen penetration into the hood component and other parts of the device can be avoided. It is. Solvent emissions from the apparatus should also be reduced as close to zero as possible. In order to be able to monitor the solvent content in the sluice chamber indicating its connection to the external atmosphere of the device, the sluice chamber is also provided with a device for monitoring the solvent concentration. As long as the oxygen and / or solvent content exceeds a set threshold that can be pre-determined and / or set, adapt the number of pumps to derivation of gas from the sluice chamber, and / or at least one It is possible to induce an additional rinsing step during the pumping cycle with an inert gas to reduce the oxygen content in the sluice chamber. For example, a long pumping cycle is provided to pump out a mixed gas atmosphere. Also, the inert gas atmosphere bell can be monitored for oxygen content and the oxygen content should be as close to zero as possible. By these means it can be ensured in an optimal manner that there is little or no oxygen contamination in the inert gas atmosphere bell of the device, in this case the optimum coating result as well as very high during product processing Safety and reliability can be achieved.

  Preferably, a cleaning and / or activation part for cleaning and / or pretreatment of the product surface and / or at least one output part for carrying the product out of the device through the water channel are provided. Preferably, the at least one cleaning and / or activating part comprises one or more sealables comprising a cleaning liquid for cleaning the product to be coated and / or an activating liquid for activating the surface or creating an adhesion promoter layer. Includes treatment tank. In such a cleaning and / or activation part, the original product can be advantageously cleaned and a blank surface of the product free of oxygen can be produced. This makes it possible to guarantee an optimum adhesive strength for subsequent coatings. To further improve the bond strength, an adhesion promoter layer can be advantageously applied to the product surface at this part of the device. By providing a process tank that can be sealed, it is possible to selectively open each product when it is planned to be inserted into each process tank. In this way, undesirable evaporation of the treatment liquid into the hood atmosphere can be further suppressed.

  Preferably, the at least one cleaning and / or activation part is arranged behind the at least one treatment tank to rinse the pre-treated product and carry over any chemical carryover from the cleaning and / or activation part. Including at least one rinsing device to prevent; Strictly speaking, when a siphon rinsing device is provided in front of the coating according to the cleaning and / or activation section, the chemistry from the cleaning and / or activation section to the siphon rinsing apparatus and to the subsequent coating electrolyte. In order to prevent any material carryover, it does not make sense to provide such a rinse of the pre-treated product. Preferably, a solvent preparation and / or regeneration device is provided and connected to such a rinsing device. The washed solvent is again recirculated to the siphon rinser, while the washed washing or activation liquid or other fluid in the treatment tanks placed before this stage is recirculated into these treatment tanks. Can circulate. For washing, distillation and subsequent storage of the washed solvent is provided.

  Preferably, at least one solvent preparation and / or regeneration device for the washing and / or activation part is provided in the detour. This allows permanent cleaning of the solvent during coating or pre-cleaning, as well as the electrolyte or other cleaning liquid and immersion liquid, and the subsequent processing section.

  Preferably, the at least one sluice chamber is or can be connected to a solvent separation and recirculation device and / or a gas oscillation system. Preferably at least one sluice chamber is provided at the inlet of the cleaning and / or activation part and / or at least one sluice chamber is provided at the outlet of the output part. Preferably, in the carry-in stage through the water channel, the product is introduced into at least one sluice chamber. The sluice chamber is then filled with an external atmosphere, sealed and subsequently evacuated so that the external atmosphere is transported from outside the chamber and is subsequently filled with inert gas. Thereafter, the product is introduced into the first processing section of the apparatus in the unloading stage through the water channel. In the unloading stage through the waterway from the device, the product is brought from the hood atmosphere into the sluice chamber, the chamber is removed from the hood atmosphere to the sluice chamber, sealed, and the hood atmosphere is pumped from it to the hood section And recirculated. The sluice chamber can continue to open and the product can be removed. The sluice chamber is then sealed again, the permeating external atmosphere is evacuated, and the chamber is filled with inert gas. Particularly preferably, a pumped sluice atmosphere is prepared, dry inert gas and washed solvent in the process, especially dry inert gas in the inert gas atmosphere bell and washed solvent in the treatment tank. Recirculated. Thus, the gas vibration system includes pumping dry inert gas into the hood atmosphere after pumping the sluice chamber atmosphere from the sluice chamber.

  Therefore, before coating, the external atmosphere is preferably brought together with the product to be coated during unloading through the water channel to the sluice chamber provided at the device outlet, and after coating the product is at the device end. Providing a solvent separation and recirculation device in the region of the sluice chamber itself proves advantageous as it is brought back to the external atmosphere by opening the sluice chamber and penetration of the external atmosphere into the sluice chamber It was done. Strictly speaking, during the loading and unloading of the product through the water channel, moisture along with oxygen can permeate the device and the evaporated solvent can leave the device. Via a preferably provided cooling device, the atmosphere pumped out of the sluice chamber and contaminated with the solvent can thus be cooled, and the solvent can be separated, collected and recycled. In the solvent separation step, the pumped gas can be dried and subsequently recirculated back to the hood atmosphere. Solvent residue adhering to the product can be removed via solvent separation in the carry-out area through the water channel, and the device can be kept almost completely dry so that almost no solvent discharge occurs. Also in the discharge area through the product channel, the solvent residues discharged during the pumping process are recondensed, collected and subsequently recycled to the process, in particular the last siphon rinse device.

  Preferably, the inert gas atmosphere bell is also cleaned, particularly by condensing the inert gas atmosphere and recirculating the condensed solvent portion to each circuit, particularly the treatment vessel. A cooling device, preferably equipped with a condensate separation device, is provided, in particular in the hood component and / or covering, and / or at least one sluice chamber, in order to recover carryover and / or evaporated solvent residues It is connected to the. Particularly preferably, the one or more cooling devices in the hood part and / or the hood component are a solvent recirculation device and / or at least one siphon rinsing device for recirculating the solvent to the treatment tank and / or the coating tank. including. Thereby, it is also possible to remove the solvent contaminants from the gas atmosphere in the hood component again. The portion of the solvent that has been condensed to the cooling device can subsequently be recirculated to the corresponding treatment tank of each hood. Since the evaporated liquid is different for each hood part and foreign substances in the gas atmosphere are always different, preferably each cooling device is usually provided in each hood part. Thus, recirculation is advantageously performed within each hood.

  Preferably, the at least one coating includes at least one coating bath that can be sealed to prevent uncontrolled evaporation of the solvent into the hood component. In particular, at least one cooling device for condensing the evaporated solvent and at least one water collecting device for collecting the condensed solvent are also provided in the gas space of the at least one coating vessel. In addition, at least one covering may include at least one output rinsing device. After the coating process, the product is put into a rinsing tank provided in the output rinsing device in order to remove the adhering electrolyte residue. In order to clean the rinsing tank, solvent separation and / or recycling of the washed solvent from the regenerator is specifically provided.

  Since the siphon rinsing device is provided to separate parts of the device, and thus in particular the cleaning and / or activation part, the processing part and the output part, it is possible to provide a substantially non-reactive solvent in these transient regions. It has proven itself advantageous. Thus, at least one siphon rinsing device is preferably filled with an inert solvent. In this way, undesirable chemical reactions that are not compatible with each other can be largely avoided. Preferably, the at least one siphon rinsing device comprises a sealable double rinsing device arranged with the upper hood section partitioned and with an attached partition. By providing such a partition immersed in the rinsing tank of the siphon device, it is possible to provide an airtight separation of the different hood parts of the device. In order to allow the product to be transported through the siphon rinse device, in particular, a particularly suitable transport device provided in the hood part cannot penetrate the partition, so in particular the product is placed laterally under the partition. At least one transporting device to be moved can be arranged or arranged in the double rinsing device so that the transporting device is located below the liquid level when the double rinsing device is filled with cleaning liquid . This ensures that the product is completely immersed in the cleaning solution, thereby cleaning the entire surface of the product to prevent carryover of chemicals and / or gas atmosphere from the front-end part to the back-end part of the equipment. And preferably can be washed with an inert rinse.

  Preferably in addition to this, at least one electrolyte / solvent separator is provided in the covering region. In particular, the electrolytic solution / solvent separation device includes a distillation device for distilling the solvent from the electrolytic solution / solvent immersion liquid discharged from at least one coating tank. In addition, an apparatus for recirculating the resulting washed solvent to the output rinse tank and / or an apparatus for recirculating the electrolyte to the electrolyte circuit is provided.

  The washing of the coating solution and thus the electrolyte solution can thus be carried out in the detour of the coating part. This cleaning device follows in particular behind the coating tank, in which the specifically cleaned solvent is recirculated to the output rinsing tank arranged after the coating tank, in particular the electrolyte to the coating tank.

  The electrolyte solution and / or solvent is preferably performed in a closed circuit. This generally avoids contamination of other tanks of the device. Advantageously, the electrolyte and / or solvent and / or rinse is washed or prepared to prevent chemical carryover. In addition to this, rinsing in various rinsing devices is preferably provided in order to prevent carryover of the electrolytic solution adhering to the product and / or the cleaning and / or activating liquid. These rinsing devices can be provided at various points in the device and coating process, particularly in the output areas of each part of the device.

  In particular, any form of product can be coated using the apparatus described in the present invention, and thus a product with a back notch on which a solvent can be deposited is also possible. With the current state of the art, such deposits cannot be removed and for this reason the solvent coating cannot be removed reliably. The method according to the invention and the apparatus according to the invention make it possible to remove the solvent residues of any form of product in a reliable manner.

  In order to describe the present invention in more detail, examples will be described in more detail with reference to the drawings. The drawing shows a comprehensive view of a metal deposition apparatus according to the present invention.

Example:
The figure shows a schematic diagram as a general view of the apparatus 1 for depositing metals and / or metal alloys. The apparatus includes a cleaning and / or activation part 2, a covering part 3 and an output part 4. In addition to this, a hood component 5 is provided that substantially hermetically surrounds all the three parts. The hood component is further divided into three parts 50, 51, 52. The three hood portions are separated from each other by the partitions 53 and 54.

  The cleaning and / or activating unit 2 includes a first sluice chamber 20, a first processing tank 21, a second processing tank 22, and a rinsing tank 23. In addition, the cleaning and / or activating unit includes a part of the first siphon rinsing device 60. The siphon rinsing device 60 is divided into two parts by a partition 53 to form a double rinsing device, which can be reached from parts 2 and 3, but otherwise forms a diffusion barrier. All tanks or cleaning devices can be sealed by respective covers 24, 25, 26, 27, 62. The sluice chamber 20 includes a sluice door 28 that allows movement of the product into the sluice chamber. Preferably such product moves to the sluice chamber via a transport carriage (not shown).

  The sluice chamber 20 is connected to a solvent recovery device 70 and a gas vibration system 80. The solvent recovery device includes a cooling trap 71, a valve 72, and a condensate separation device 73, a conduit 74 between the valve 72 and the sluice chamber 20, and a conduit 75 between the cooling trap 71 and the condensate separation device 73. And a recirculation circuit 76 between the condensate separator 73 and the first treatment tank 21.

  The gas vibration system 80 includes a vacuum pump 81, three valves 82, 83, 84, a conduit 85 between the sluice chamber 20 and the first valve 82, and an additional connection between the valve 82 and the vacuum pump 81. It includes an additional line 88 between the valve 83 and the hood component 50, as well as a line 87 between the line 86, the vacuum pump 81 and the valve 83 in the recirculation line to the hood component. Line 87 also leads to valve 84, from which additional line 89 leads to the outside atmosphere. Through this, air can be blown out of the device.

  In addition, the solvent preparation and / or regeneration device 90 is connected to the cleaning and / or activating unit 2. The solvent preparation and / or regeneration device includes a distillation device 91 and a condensate water collection tank 92. The distillation apparatus is supplied via a conduit 93 from the rinsing tank 23. A conduit 94 is also provided between the distillation apparatus 91 and the condensate water collection tank 92. The cleaning liquid cleaned in the distillation apparatus 91 is recirculated to the second treatment tank 22 through the pipe line 95, the pump 96 and the additional pipe line 97. The clean solvent distilled by the distillation apparatus can be pumped back from the condensate water collection tank 92 to the rinsing tank 23 via the pipe line 98, the pump 99 and the pipe line 100.

  In addition, if necessary, an overflow line 29 is provided between the rinsing tank 23 and the second processing tank 22 in order to avoid overflow of the rinsing tank when an excessive amount of solvent is recycled. Is provided.

  The excess solvent is then recycled to the second treatment tank 22 via the overflow line 29.

  In addition, the hood part 50 of the cleaning and / or activation part 2 includes a transport device 55 that traverses the product 7 between each treatment, rinse and other tanks. For this purpose, the transportation device includes a transportation carriage 56 provided with a hook 57 for suspending the product 7 to be coated in this embodiment. Here, since the hook 57 is fixed on the transport carriage 56 and can be moved laterally, the product on the hook can be slowly lowered to each tank and can be lifted therefrom.

  In addition, the hood unit 50 includes a cooling device 58. In the figure, it is shown in the form of a cooling coil. Via the cooling coil, the evaporated solvent can be condensed and collected in the water collecting device 59 provided in the hood unit 50 as well. In the figure, the water collecting device is shown in the form of a water collecting trough. The solvent collected in the water collection trough or the water collection device 59 can be recirculated to the first coating tank 21 via the drain line 101. Thus, there may be first and second coating baths of solvent. In principle, more coating vessels can be provided, but this figure only reproduces one possible embodiment. It is also possible to provide several rinsing tanks. Similarly, in principle, it would be possible to provide more than two sluice chambers.

  In order to be able to maintain a uniform pressure in the hood 50, the gas buffer container 120 has a hood configuration despite the cleaning of the gas in the hood and the recirculation of the cleaned gas. It is provided outside the material 5.

  The gas buffer container 120 is connected to the inside of the hood unit 50 via the pipe line 121. Two-way exchange of gas is performed between the gas buffer container and the hood unit 50 through the pipe line 121. This makes it possible to maintain a preset overpressure and in particular a constant pressure in the hood part.

  In order to check the oxygen and solvent contents in the cleaning and / or activating unit 2, the second oxygen sensor 123 and the solvent concentration sensor 124 in the sluice chamber 20 together with the first oxygen sensor 122 in the hood unit 50 region. Is provided. All sensors can be connected to a monitoring and control device (not shown) to monitor the set threshold overshoot and selectively adapt the sluice chamber pumping cycle and gas exchange as needed. .

  The covering 3 includes a second part of the siphon rinse device 60 which is formed as a double rinse device as described above. For the transport of the product brought into the siphon rinsing device 60 via the cover 62, the siphon rinsing device 60 is provided with a transport device 66 which can be equipped with a transport carriage as shown. After transportation through the siphon rinsing device, the product can be taken out on the side of the covering portion 3 through the cover 63 of the siphon rinsing device 60. The covering part 3 includes a first part of an output rinsing tank 32 and an additional siphon rinsing device 61 together with two coating tanks 30, 31. Each of these tanks is provided with covers 33, 34, and 35, while the siphon rinsing device is provided with a cover 64 on the covering portion side. In the gas space below the covers 33, 34 of the two coating vessels 30, 31, there are cooling coils for condensing and evaporating the solvent evaporating from the electrolyte into the rinsing bath 32 during the coating and especially after the coating bath. 38 and 39 and water collecting troughs 38 and 39 are provided, respectively.

  In addition, the coating unit 3 is provided with a cleaning device connected to the coating unit in order to clean the electrolytic solution in the detour of the electrolytic solution / solvent separation device 110. This ensures that there is no significant amount of electrolyte carry over, thereby producing a generally closed material circuit. In order to wash the electrolyte, the fluid is led from the two coating tanks 30, 31 to the distillation device 112 via the conduit 111. In addition to this, a condensate water collection tank 113 is provided and connected to the distillation apparatus 112 via a pipe line 114. The washed electrolyte is recirculated to the coating tank 30 via the pipe lines 115 and 117 and the pump 116. Solvent distilled from the electrolyte / solvent mixture is collected in the condensate water collection tank 113 and recirculated through line 118, pump 119 and recirculation line 102 to the rinse tank in the output rinse tank 32. . Thus, the rinsed solvent in the output rinsing tank 32 is always supplied with the washed solvent. When the water level of the output rinsing tank rises too much, an overflow line 103 is provided between the output rinsing tank and the second coating tank 31. Through this overflow line, excess rinsing liquid, and in particular the solvent, returns to the second coating tank.

  Similar to the cleaning and / or activation part 2, the covering part 3 also has a transport device 55 with a transport carriage 56 and a hook 57 so that the product 7 to be coated can be transported between each tank of the covering part. Including. In addition to this, a water collecting trough is provided as a water collecting device 59 for the condensed solvent together with a cooling device 58 in the form of a cooling coil. The collected condensed solvent is recycled to the first coating tank 30 via the drain line 104.

  Outlet portion 4 includes a second portion of siphon rinse device 61. This is provided with a transport device 67 as well as the transport device 60. Through this, the product brought into the siphon rinse device via the cover 64 is transported to the other side of the partition 54 and to the part of the siphon rinse device 61 having the cover 65. As in the siphon rinsing device 60, the transport takes place below the level of the rinsing liquid in the siphon rinsing device. This makes it possible to eliminate gas almost completely during the transport of the product from the covering part to the output part.

  In addition, the output includes a second sluice chamber 40 that carries the coated product out of the device through a water channel. A cover 41 is provided in the sluice chamber. In addition, a sluice door 42 is included. Similar to the sluice chamber 20, the sluice chamber 40 is provided with an apparatus 130 for recovering the solvent and a gas vibration system 140. The apparatus for recovering the solvent also includes a cooling trap 131, a valve 132 between the sluice chamber 40 and the cooling trap 131, a condensate separation device 133, a pipe line 134 between the valve 132 and the sluice chamber 40, and a condensate separation device. A conduit 135 between 133 and the cooling trap 131 and a solvent recirculation conduit 136 between the condensate separator 133 and the siphon rinse device 61 are provided.

  The gas vibration system 140 includes a vacuum pump 141, three valves 142, 143, and 144 and several lines disposed therebetween. The first line 145 leads from the sluice chamber 40 to the first valve 142, and the second line 146 leads from the valve 142 to the pump 141. For this purpose, a pipe line from the cooling trap 131 is connected in the same manner as in the device 70 between the cooling trap 71 and the vacuum pump 81. A pipe 147 is connected to the valve 143 from the pump 141, and a recirculation pipe 148 is connected to the hood portion 52 therefrom. Further, the pipe line 147 is connected to the valve 144 from the vacuum pump, and in particular, air from the sluice chamber 40 can be blown outside through the pipe line 149.

  The hood 52 also includes a transport device 55 with a transport cart 56 that includes hooks 57 for catching the product 7 and lowering it from each tank. Similarly, a cooling coil 58 is provided as a cooling device, and a water collection trough 59 is provided for the condensed solvent that can be recirculated from the water collection trough through the inlet line 105 to the siphon rinse device 61. Is done.

  The output unit 4 is also provided with a gas buffer agent container 125 and a pipe 126 between the inside of the hood unit 52 and the gas buffer agent container 125. This ensures that as constant a gas pressure as possible is maintained at the output. Of course, just after the pumping of the finished product from the sluice chamber 40 from the external atmosphere after the unloading process through the water channel, the underpressure while the hood atmosphere from the output unit is loaded into the sluice chamber 40 through the water channel Similarly, overpressure can be generated in the hood section of the output section, for example, by recirculating dry inert gas through line 145.

  Specifically, oxygen and solvent content in the output section in a continuous manner as much as possible due to the constant opening and closing of the output section to carry the finished product through the water channel and recirculate the purified gas To determine the amount and intervene to correct as necessary, and thus to avoid as much as possible undesirable solvent emissions from the sluice chamber, and to minimize solvent loss and harmful emissions from the equipment In order to maintain, first and second oxygen sensors 127, 128 and a solvent concentration sensor 129 are provided. A first oxygen sensor 127 is provided in the upper hood portion 52, while a second oxygen sensor 128 and a solvent concentration sensor 129 are provided in the sluice chamber 40. Further, such an oxygen sensor 150 is provided in the hood portion 51 above the covering portion 3.

  The coating process in each regeneration step of the electrolytic solution, cleaning solution, solvent, and gas atmosphere will be described in more detail below.

  The product to be coated is brought into the first sluice chamber 20 via the sluice door 28. This is done in particular via a transport carriage, which is not shown. During the loading process through the passage, the sluice chamber is inevitably filled with an external atmosphere (air) and subsequently sealed. The sluice chamber is then evacuated via vacuum pump 81 and lines 85 and 86. For this purpose, the valve 82 is opened. Thereafter, the only uncontaminated air is present in the sluice chamber and can therefore be discharged directly to the outside via the line 89 and the open valve 84. Subsequently, the sluice chamber is filled with an inert gas from the hood section 50. Immediately thereafter, the inner cover 24 disposed between the sluice chamber and the hood portion 50 can be opened, and the product can be brought into an inert gas atmosphere. Since the sluice chamber can finally be evacuated to less than 1 to 2 mbar, the amount of oxygen that can penetrate the first hood portion 50 is very small, and further intermediate rinsing with inert gases, especially nitrogen and oxygen Is also possible.

  Depending on the amount of gas required for inflow and withdrawn from the hood section 50, a pressure drop will likely occur if a gas buffer container is not provided. In order to avoid this and prevent new traces of oxygen and water from being found in the hood part, for example, a new inert gas such as nitrogen must be constantly brought into the hood part. Is connected to the hood part 50, and the volume may change, so that the pressure in the hood part 50 is maintained substantially constant.

  Monitoring of the atmosphere in the hood part can be constantly performed by an oxygen sensor. The solvent concentration is monitored via a solvent concentration sensor 124. Confirming the dispersion of oxygen in the system makes sense especially with respect to the service life and coating properties of the electrolyte, but it also makes sense for the overall reliability of the process and the overall operational safety of the system. ing.

  After the product is brought into the hood 50 through the cover 24, the cover 24 is closed again and the sluice atmosphere can be pumped, where the inert gas / solvent mixture is present and pumped out. . This is done after opening the valve 72 via line 74, so that the inert gas / solvent mixture is directed via the cold trap 71. After the condensation, the obtained dry inert gas is recirculated to the hood section 50 through the vacuum pump 81, the pipe line 87, then the open valve 83 and the pipe line 88. The inert gas can be used as a cleaned gas in the atmosphere in the hood unit 50 again. By collecting the excessive gas volume due to the increase in the volume in the gas buffer container 120, the pressure in the hood portion 50 can be kept substantially constant.

  The condensed solvent that accumulates is introduced into the condensate separator 73 via line 75 and is recycled to the first treatment tank 21 via the solvent recirculation line 76 in a particularly regenerated manner. Can circulate. Subsequently, fresh inert gas flows back into the evacuated sluice chamber, and the door to sluice door 28 or sluice door 28 can be reopened to bring a new product into the apparatus.

  In order to ensure that the product can be brought into the treatment tanks 21, 22, in particular containing the cleaning liquid, via the transport device 55, and can be precleaned there, and in the subsequent coating, in particular. Blank oxygen-free surfaces can be produced. In addition, an adhesion promoter layer can be applied on top of it in the bath. Covers 25 and 26 are provided to generally avoid evaporation of the solvent. Similarly, a cover 27 is provided on the rinsing tub which is preferably opened only when goods or products are brought in or taken out. The rinsing tank 23 disposed after this serves the purpose of avoiding the carryover of chemicals from the processing tanks 21 and 22 to the siphon rinsing device 60, and here, the rinsing tank 23 is applied to the coating electrolyte in the tank in the coating portion. Carryover should also be avoided. The liquid in the rinsing tank 23 is periodically prepared via a solvent preparation and / or regenerator 90 connected to the detour to the cleaning and / or activation section.

  After rinsing the pretreated product, it is put into the siphon rinsing device 62 through the cover 62. Since the partition 53 is provided, the two hood parts 50 and 51 existing above are separated from each other in an airtight manner, but are still connected to each other by the double rinsing device of the siphon rinsing device 60. The product can pass through. Preferably the liquid in the siphon rinsing device is the same as the solvent used in the coating electrolyte. In order to avoid reaction with the cleaning solution and / or the coating electrolyte as much as possible, an inert solvent is preferably used. By providing a siphon rinsing device between the activation part 2 and the covering part 3, this advantage prevents all movement of the solvent to the electrolyte region via the gas atmosphere in the cleaning and activation part. Therefore, a solvent having poor compatibility with the coating electrolyte can be used. In particular, the carry-over of the solvent accompanying the product to be coated can be most substantially prevented by preparing the liquid in the rinsing tank 23 via the distillation apparatus 91.

  After the product has been raised through the cover 63 of the siphon rinsing device 60, the product can reach the coating part 3 and can be raised therein to the coating baths 30,31. In addition to the two coating tubs shown in the tub, a number of additional tubs can be provided as well as the additional output rinsing tub 32, but only one of them is shown in the figure. In order to avoid uncontrolled evaporation of the solvent in the upper hood 51, the covers 63, 33, 34, 35 and 64 are closed in normal operation. Preferably, the cover is only opened to move or remove the product from each tank.

  In the two coating tanks 30 and 31, the cooling coils 36 and 37 and the water collection troughs 38 and 39 are located in the gas space between the liquid level of the tank and the cover, respectively. Here, the solvent evaporated from the electrolytic solution during the coating is condensed and led to the rinsing tank in the output rinsing tank 32. A relatively large amount of electrolytic solution is periodically supplied to the reaction through a distillation apparatus provided in the electrolytic circuit, and is pumped back to the tank 30 through a pipe line and a pump 116 provided therebetween. Solvent distilled from the electrolyte is collected in the water collection tank 113 and recirculated again to the output rinsing tank 32 or to the rinsing tank inside it via a line and pump 119. To avoid overflow of the output rinse tank 32, excess solvent is recycled to the circuit or tank 31 via the overflow line 103. This ensures that a significant amount of electrolyte is not carried over to the additionally placed siphon rinse device 61, and even at this point a material circuit that is already largely closed can be produced.

  The siphon rinsing device 61 connecting between the sheath and the output is comparable to the siphon rinsing device 60 in structure and function. The product completely immersed therein is taken out again through the cover 65 on the output unit 4 side. Due to the previous rinsing in the output rinsing tank 32 containing fresh solvent, the electrolyte residue adhering from the coating part 3 is collected and not carried over to the output part 4. In addition, each output rinse tank also serves to effectively utilize and remove excess processing heat generated during the coating process from the system.

  The output unit 4 is also provided with a second sluice chamber to carry the coated product. This is done via the cover 41. After storing the final coated product in the sluice chamber, the pumping process is also started. This serves to recover the solvent residue still adhering to the coated product. This allows the fully coated product to leave the device in a dry state and almost no solvent drain can occur. Any solvent that evaporates during the pumping process, is recondensed in the cold trap 131 and is collected in the condensate separator 133 is recirculated to the siphon rinse device 61 via line 136. Otherwise, the unloading process through the passage operates in the same way as the unloading process through the passage with respect to sluice atmosphere and inert gas pumping and pumping. The sluice door 42 is opened for the purpose of carrying out through the passage.

  Each hood 50, 51 and 52 is filled with inert gas and at least in this embodiment is kept constant at a slight overpressure rather than the ambient atmosphere via an automatic pressure maintenance system. This avoids any air penetration into the hood components. Oxygen sensors 122, 123, 127, 128, and 159 constantly indicate the oxygen content in each gas atmosphere. When a predefined threshold is exceeded, pump time adaptation is performed for pumps 81, 141, or additional rinsing is initiated by an inert gas during the pumping cycle in sluice chambers 20, 40. Is done.

  Also, by filling the siphon rinse device with a barrier liquid, particularly an inert solvent, an additional barrier effect in this region is provided, especially in the combination of the covers 62, 63 and 64, 65, so that Additional reduction of oxygen and moisture diffusion is possible. The combination of sluice chamber, vacuum system, gas vibration system and siphon rinsing device can effectively suppress or largely prevent the formation of undesired reaction products such as alkoxy compounds or aluminum oxane, so that the metal organic coating electrolyte Provides a very long service life and uniform coating quality.

  By providing a solvent preparation for the cleaning and / or activating unit 2, it is used in carryover of other chemicals with oxygen and moisture, especially in cleaning solutions that are incompatible with the given coating electrolyte It is possible to effectively prevent the solvent from being mixed into the coating electrolyte due to carry-over. Providing the solvent preparation and / or regenerator 90 allows direct recirculation of the cleaning solution and solvent to the corresponding circuit. This maintains the contamination in the rinsing tank 23 at a very low level.

  By condensing the hood atmosphere in the hood parts 50, 51, 52, the hood part can be kept as dry and pure as possible. Also, the product that evaporates during the transit time, especially when the product is still warm, the solvent residue found on the product will be condensed in a controlled manner and recirculated back to each material via the drain line. Can do.

  In addition to the embodiments described above and shown in the drawings, many other forms can be formed, each of which keeps the discharge of solvent from the apparatus as low as possible and other contaminants along with oxygen and moisture. It is possible to achieve the greatest possible reduction in carryover to the coating electrolyte and thus extend the service life of the coating electrolyte while avoiding the formation of undesirable reaction products. In particular, only one or more than two treatment layers, coating tanks, siphon rinsing devices and rinsing tanks can be provided. In addition, additional parts, in particular additional coverings, can be provided. The siphon rinsing device can also be replaced by another device with a corresponding action, in which a gas-related separation between the parts of the device is also possible. In principle, it is also possible to make the cleaning and / or activation part smaller or even to omit it completely. In either case, the apparatus forms a generally sealed bell above each station of the coating apparatus, and at the same time there is a constant cleaning of the treatment tank or coating tank and rinse tank along with the atmosphere. This can be achieved in a particularly simple manner by directing the cleaning section in the detour to each processing section or processing section. Alternatively, more complex cleaning procedures or circuits are possible.

1 shows a schematic diagram as a general view of an apparatus 1 for depositing metals and / or metal alloys.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Apparatus 2 Cleaning | cleaning and activation part 3 Covering part 4 Output part 5 Hood component 7 Product 20 1st sluice chamber 21 1st process tank 22 2nd process tank 23 Rinse tank 24 Cover 25 Cover 26 Cover 27 Cover 28 Sluice door 29 Overflow line 30 First covering tank 31 Second covering tank 32 Output rinsing device 33 Cover 34 Cover 35 Cover 36 Cooling coil 37 Cooling coil 38 Water collecting trough 39 Water collecting trough 40 Second sluice chamber 41 Cover 42 Sluice door 50 1st hood part 51 2nd hood part 52 3rd hood part 53 Partition 54 Partition 55 Transport device 56 Transport cart 57 Hook 58 Cooling device 59 Water collecting device 60 First siphon rinse device 61 Second siphon Rinse device 62 Cover 63 Cover 64 Cover 65 Cover 66 Transport device 67 Transport device 70 Solvent recovery device 71 Cooling trap 72 Valve 73 Condensate separation device 74 Pipe line 75 Pipe line 76 Solvent recovery circuit 80 Gas vibration system 81 Vacuum pump 82 Valve 83 Valve 84 Valve 85 Pipe line 86 Pipe line 87 Pipe Line 88 Pipe line 89 Pipe line 90 Solvent preparation and / or regeneration device 91 Distillation device 92 Condensate collection tank 93 Pipe line 94 Pipe line 95 Pipe line 96 Pump 97 Pipe line 98 Pipe line 99 Pump 100 Pipe line 101 Drain line 102 Recirculation Line 103 Overflow Line 104 Drain Line 105 Drain Line 110 Electrolyte / Solvent Separator 111 Line 112 Distiller 113 Condensate Water Collection Tank 114 Line 115 Line 116 Pump 117 Line 118 Line 119 Line 120 Gas buffer container 121 Line 122 First oxygen sensor 123 Second oxygen sensor 124 Medium concentration sensor 125 Gas buffer container 126 Pipe 127 First oxygen sensor 128 Second oxygen sensor 129 Solvent concentration sensor 130 Solvent recovery device 131 Cooling trap 132 Valve 133 Condensate separator 134 Pipe 135 Pipe 136 Solvent recirculation line 140 Gas vibration system 141 Vacuum pump 142 Valve 143 Valve 144 Valve 145 Pipe line 146 Pipe line 147 Pipe line 148 Pipe line 149 Pipe line 150 Oxygen sensor

Claims (25)

Depositing a metal and / or metal alloy, in particular a metal-organic complex salt in an organic solvent, from the metal-organic electrolyte on the product (7) and at least one coating (3) covering the product (7), at least one Including an additional processing section (2, 4) and at least one sluice chamber (20, 40) for carrying the product (7) into and out of the apparatus (1) through a water channel, generally without oxygen and / or moisture penetration. A siphon rinsing device (60, 61) separates the gas from the other part (2, 4) of the device from the covering (3) or of these other parts (2, 4) relative to the covering (3). Separation device (53, 54) for sealing, as well as an inert gas and covering (3), at least one siphon rinsing device (60, 61) and at least one additional covering ( A device (1), characterized in that at least one hood component (5) is provided which generally seals 2, 4). In the siphon rinsing device, at least one transport device (66, 67) for moving the product laterally below the partition (53, 54) is or can be arranged, so that the siphon rinsing device (66, 67). The device (1) according to claim 1, characterized in that the transporting device (66, 67) is positioned below the liquid level during the filling with the rinse liquid. At least one oxygen monitoring device is provided in at least one sluice chamber (20, 40) and / or part (50, 51, 52) of the hood component (5) and / or monitors the solvent concentration. Device (1) according to any of the preceding claims, characterized in that one device (124, 129) is provided in the sluice chamber (20, 40). Immediately after the settable or set threshold is exceeded, at least one oxygen monitoring device is adapted to adapt the pump time to the introduction and discharge of gas into the sluice chamber (20, 40) and / or to at least one sluice chamber ( 20. The device (1) according to claim 3, characterized in that it induces an additional rinsing step with an inert gas during the pumping cycle to reduce the oxygen content in 20, 40). At least one pressure maintenance device is provided which maintains a constant pressure in the hood component (5) and / or a slight overpressure in the hood component (5) than the outside or ambient atmosphere, in particular a hood component ( 5) and / or in order to maintain a substantially constant pressure in the hood part (50, 52), at least one gas buffer (120, 125) is provided and / or in particular the first of the device (1). Device (1) according to any of the preceding claims, characterized in that it is connected to or capable of being connected to one (2) and / or the last part (4). Device (1) according to any of the preceding claims, characterized in that at least one cleaning and / or activation part (2) for cleaning and / or pre-treating the surface of the product (7) is provided. ). The at least one cleaning and / or activation part (2) comprises a cleaning liquid for cleaning the product (7) to be coated and / or an activation liquid for activating the surface, in particular for producing an adhesion promoter layer. One or more sealable treatment tanks (21, 22) and / or at least one cleaning and / or activating part (2) cleans and / or cleans the pretreated product (7). Alternatively, it comprises at least one rinsing device (23) arranged behind the at least one treatment tank (21, 22), preventing carryover of chemicals from the activation part (2), Apparatus (1) according to claim 6. At least one coating (3) is sealable (33, 34) at least one coating bath (30, 31) and / or coating to prevent uncontrolled evaporation of the solvent to the hood component (5) Device (1) according to any of the preceding claims, characterized in that it comprises at least one output rinsing tank (32) for rinsing the processed product. At least one solvent preparation and / or regeneration device (90), in particular at least one solvent preparation device (90) for one cleaning and / or activation part (2), is provided in the detour. A device (1) according to any of the preceding claims. At least one sluice chamber (20, 40) is connected to or connectable to a solvent separation and recirculation device (70, 130) and / or a gas oscillation system (80, 140), Device (1) according to any of the preceding claims. At least one cooling device (36, 37, 58, 71, 131) with a condensate separation device (38, 39, 59, 73, 133) for carryover and / or recovery of evaporated solvent residues; Any of the preceding claims, characterized in that they are provided in particular in the hood component (5) and / or the covering (3) and / or connected to at least one sluice chamber (20, 40) (1). Including a solvent recirculation device (101, 104, 105) for recycling the solvent to the treatment and / or coating bath (21, 22, 30, 31) and / or including at least one siphon rinsing device (61) At least one cooling device (36, 37) for condensing the evaporated solvent, and at least one water collecting device (38) for collecting the solvent condensed in the gas space of the at least one coating vessel (30, 31). ) 39) including one or more cooling devices in the hood part (50, 51, 52) and / or hood component (5). The device (1) described. At least one electrolyte / solvent separator (110) is provided in the region of the coating (3), in particular the electrolyte / solvent separator (110) is discharged from at least one coating vessel (30, 31). There is provided a device (102, 114, 118) comprising a distillation device (112) for distilling the solvent from the liquid / solvent soak, and in particular for recycling the resulting clean solvent to the output rinse tank (32). Device (1) according to any of the preceding claims, characterized in that: At least one sluice chamber (20) is provided at the inlet of the cleaning and / or activation part (2) and / or at least one sluice chamber (40) for carrying the product (7) through the passage. A device (1) according to any of the preceding claims, characterized in that it is provided at the outlet of the output part (4). Device (1) according to any of the preceding claims, characterized in that the hood component (5) comprises at least one transport device (55) for laterally moving the product between the respective tank and device. . Device (1) according to any of the preceding claims, characterized in that at least one siphon rinsing device (60, 61) is filled with an inert solvent. A method of depositing a metal and / or metal alloy, in particular a metal organic complex salt in an organic solvent, onto a product (7) from a metal organic electrolyte,
The following steps:
Depositing metal and / or metal alloy through at least one sluice chamber (20), in particular through the water-free channel of the product (7) to the device (1) according to any of the preceding claims. Carried in and out,
Transferring the product (7) to the at least one coating (3), generally excluding gas,
Coating the product (7) in at least one coating (3);
Transferring the coated product (7) from the coating (3) via the at least one siphon rinsing device (61) to the at least one output (4) in a generally excluded manner, and a finished product ( 7) through the water channel via at least one additional sluice chamber (40), where the inert gas atmosphere bell is maintained above all parts (50, 51, 52) of the device. A method characterized by comprising. 18. Method according to claim 17, characterized in that the product has been pretreated, in particular its surface has been cleaned and / or activated for further treatment. After cleaning and / or activation, the product is introduced via the at least one additional siphon rinsing device (60) into the at least one covering part (3) with a substantial elimination of gas. The method of claim 18. The electrolyte and / or solvent is led to a generally closed circuit, in particular there is a cleaning or preparation of the electrolyte and / or solvent and / or rinsing solution to avoid chemical carryover The method according to any one of claims 17 to 19. 21. A method according to claim 17, characterized in that they are rinsed in a rinsing device (23, 32) in order to avoid carry-over of cleaning and / or activation and / or electrolytes adhering to the product. The method in any one of. In the carrying-in process through the passage, the product is introduced into at least one sluice chamber (20, 40), the sluice chamber (20) is filled with an external atmosphere, sealed and subsequently evacuated, and the external atmosphere is carried out of the chamber. 22. Method according to any of claims 17 to 21, characterized in that the chamber is subsequently filled with an inert gas and the product is subsequently brought into the first processing part (2) of the apparatus. A pumped sluice atmosphere is prepared, the dry inert gas and the washed solvent are in the process, in particular the dry inert gas is in the inert gas atmosphere bell, and the washed solvent is in the first treatment tank (21 23. The method of claim 22 wherein the method is recycled to At least one sluice chamber atmosphere is monitored for oxygen and / or solvent inclusions and / or an inert gas atmosphere bell is monitored for oxygen inclusions, particularly for the discharge of contaminated atmospheres immediately after a set threshold is exceeded and / or 24. A method according to any of claims 17 to 23, characterized in that the introduction of the cleaned inert gas atmosphere is accelerated or decelerated. 25. The gas of an inert gas atmosphere bell is also cleaned, in particular by condensing the gas and recycling the condensed solvent part to each material circuit. the method of.

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