EP1611270A2 - Procede et dispositif pour reguler au moins une grandeur d'exploitation d'un bain electrolytique - Google Patents

Procede et dispositif pour reguler au moins une grandeur d'exploitation d'un bain electrolytique

Info

Publication number
EP1611270A2
EP1611270A2 EP04723967A EP04723967A EP1611270A2 EP 1611270 A2 EP1611270 A2 EP 1611270A2 EP 04723967 A EP04723967 A EP 04723967A EP 04723967 A EP04723967 A EP 04723967A EP 1611270 A2 EP1611270 A2 EP 1611270A2
Authority
EP
European Patent Office
Prior art keywords
sample
bath
concentration
arrangement
determining
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP04723967A
Other languages
German (de)
English (en)
Inventor
Harald Engler
Jochen Heinzinger
Konrad Jung
Klaus D. Rathjen
Matthias Schmidt
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
MTU Aero Engines AG
Original Assignee
MTU Aero Engines GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by MTU Aero Engines GmbH filed Critical MTU Aero Engines GmbH
Publication of EP1611270A2 publication Critical patent/EP1611270A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/12—Process control or regulation
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/12—Process control or regulation
    • C25D21/14—Controlled addition of electrolyte components
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00—Chemistry: analytical and immunological testing
    • Y10T436/12—Condition responsive control

Definitions

  • the invention relates to a method for controlling at least one operating variable of an electrolytic bath according to the preamble of claim 1 and a device for carrying out the method according to the preamble of claim 7.
  • Galvanic processes are used to manufacture workpieces with coatings for corrosion protection, for decorative purposes and to prepare a paint job.
  • a galvanizing system consists of a series of active baths, in each of which an electrolytic coating process takes place, and each active bath of at least two rinsing baths, with at least one rinsing bath generally being operated as a circulating rinsing bath.
  • the operating parameters of the processes running in the baths must be controlled and / or regulated. If processes are controlled manually by an operator according to their wealth of experience, then there are strong fluctuations in the process conditions, which leads to changing qualities of the galvanized products and to a high consumption of process materials and process auxiliaries.
  • the bath compositions are monitored by means of concentration measurements on samples, manual sampling and external sample analysis being time-consuming and cost-intensive and no simultaneous control of the galvanizing operation being permitted.
  • the composition of the active baths has a direct influence on the quality of the coatings. If the concentrations of the active substances, such as chromium, nickel or zinc, in the active baths are too low, the metals are deposited incompletely and with insufficient layer thicknesses. The active baths also accumulate due to carryover from previous baths and as a result of chemical reactions of the workpieces with foreign ions. The result of this is that the layers to be deposited become inhomogeneous and the inorganic corrosion protection or the preparation for organic corrosion protection is no longer sufficient.
  • the rinsing baths serve to rinse the previously galvanized workpieces. This is to avoid carry-over with foreign ions in the subsequent process steps or into the environment. Rinsing baths are processed using ion exchangers or reverse osmosis. Their treatment results in considerable amounts of waste water and sludge. The extracted chemicals and water have to be fed back into the electroplating plant as educts, which is uneconomical and ecologically questionable. This is particularly true when the rinsing baths are operated as circuit rinsing with a constant high volume flow for reasons of a sufficient rinsing effect. It is known to control the composition of the rinsing bath according to the degree of contamination. With manual sampling from the rinsing baths, the disadvantages described for the active baths arise.
  • DE 197 36 350 Cl describes a method for regulating the concentration of substances in electrolytes, in which the content of oxidized redox ions in an auxiliary electrolytic cell is reduced to the extent that metal is dissolved in the electrolyte by the oxygen introduced.
  • the metal content is regulated via the adjustable current of the auxiliary cell, so that the overall electrolytic system is in equilibrium. Signals of an analyzer for determining the metal ion content of the metal to be deposited in the electroplating system can be fed to the current regulator of the auxiliary cell.
  • the process for the electrolytic deposition of metals from electrolytes according to DE 44 05 741 Cl uses additives from process organics to achieve certain physical properties.
  • the organic additives are added continuously.
  • a vaccination point in the piping system of an electrolyte circuit in the vicinity of an electrolytic cell can be selected as the dosing location. With the help of porous partition walls, it is ensured that the process organics are only in the cathode compartment, which is free from the aggressive oxidized stage of the redox agent.
  • DE 197 27 939 AI describes a method for dosing rinsing liquid, in which the weight of a carried-over amount of solution is determined by weight measurements on the object to be galvanized and, if appropriate, on the carrier of the object. The resulting changes in concentration in the respective bath stations can be calculated from the measured carry-over measurements.
  • a data processing system is used, to which a control or regulating circuit for rinsing water metering is connected, so that slightly changed solution concentrations can be automatically adjusted to a target value.
  • JP 11118796 A shows an arrangement for analyzing proteins in the urine, in which a urine sample is mixed with a diluent and a coloring agent and fed to an optical scattered light analyzer via lines. The sample liquid is exposed to laser light in the scattered light analyzer. The composition of the scattered light changes depending on the protein content of the sample liquid. The analysis time and the amount of sample liquid are changed depending on the absorption of the measuring light.
  • the substance analysis methods listed are the examination of individual samples that are prepared at the location of the analysis arrangement and are fed to the analysis arrangement.
  • the analysis arrangements are regarding the handling of the samples and regarding the interaction with control and regulating devices not trained for the process control of electroplating systems.
  • the object of the invention is to develop a method and a device for controlling at least one operating size of an electrolytic bath, which allow the production of coatings with improved quality, the use of chemicals being reduced.
  • the method for controlling at least one operating variable of an electrolytic bath is based on the concentration measurement of a bath component with electromagnetic radiation, which excites a sample taken from the bath in such a way that light is emitted.
  • the concentration can be determined from the spectrum of the emitted light.
  • Various operating variables can be controlled or regulated using the concentration measurement values obtained.
  • company size refers here to all physical quantities, the change of which influences the quality of a coating and the amount of chemicals used.
  • Important operating parameters are, for example, the bath composition, the bath temperature, the movement of the electrolyte and the objects to be galvanized, the degree of contamination or the electrical current in a bath.
  • a galvanizing system is controlled or regulated with the aid of process-integrated analytics, the analytics preferably being based on laser-induced emission spectral analysis.
  • the contamination of a galvanic bath or a rinsing bath can advantageously be checked with the laser-induced emission spectral analysis.
  • An arrangement for laser-induced emission spectral analysis preferably contains a laser with which a liquid sample taken from the bath is vaporized by a number of laser pulses. The amount of liquid is small, for example with a volume of less than 1 ml.
  • the ionogenic composition of the liquid constituents is determined using a downstream spectrometer. It is essential that the non-contact measurement method has no or only a low sensitivity to contamination with foreign ions.
  • the measuring procedure allows a quick bath analysis without an expensive sample preparation.
  • a measurement time of less than. three seconds can be realized, which is a quasi-simultaneous detection of the state of a bath.
  • a sample digestion is not necessary.
  • the time-resolved measurements of the concentrations can take place in an air atmosphere without using a protective gas.
  • the spectroscopic measurement values are transferred to a computer which is part of the control or regulation of the electroplating system.
  • manipulated values for actuators are generated which, for. B. controls the resharpening or draining of an active bath when the specified concentrations of active bath or interfering substance substances are exceeded or fallen below.
  • the control of the rinsing bath regeneration i.e. the volume flow to be regenerated, is possible. This minimizes the consumption of energy, processing aids, such as flocculants and precipitants, and of water and wastewater.
  • samples are fed from each bath separately to the spectrometer in a decentralized piping system.
  • good mixing it is advantageous if high flow velocities of the sample liquid are achieved in the pipes of the piping system.
  • the piping system can be provided inexpensively with small flow cross sections. The Separate piping system saves time-consuming and costly intermediate cleaning of the pipelines with distilled water and subsequent drying with compressed air, which would be necessary if all baths were connected to the spectrometer via only one sample feed.
  • the piping system ends at a sample plate, wherein the sample liquid from a specific bath can be timed and automatically sprayed onto the sample plate.
  • a sample plate can be designed as a carousel for individual samples, with laser light acting directly on a sample on the sample plate. After analyzing the light emanating from the sample, the sample is removed from the sample plate with appropriate cleaning devices and the sample plate is loaded with a fresh sample. Samples of only one bath can be brought on the sample plate as well as samples from different baths.
  • the spectroscopic measurement values obtained can be transmitted directly to a master computer in the electroplating system for calculating control values.
  • the measurement data can be saved for archiving the bath conditions, in particular the active bath conditions. It is possible to record the time dependence of the concentrations and to detect concentration intervals.
  • the method and the device allow "process-integrated detection, in particular of aluminum, copper, cadmium, chromium, iron and zinc, and of further elements in active and / or rinsing baths. It is possible to concentrate the substances mentioned in the active baths in area 1 -lOOg / l and in the rinsing baths in the area below lOOppm.
  • FIG. 1 shows a diagram of an electroplating system for carrying out the method.
  • the electroplating system consists of two containers 1, 2 for active baths 3, 4 and four containers 5-8 for rinsing baths 9-12, each of which is arranged downstream of the active baths 3, 4 in the process sequence.
  • the knitting baths 3, 4 each dissolved salt of a coating metal.
  • the workpieces 13 to be coated hang on carrying devices 14 which are connected to conveyors.
  • the workpieces 13 are completely immersed in an active bath 3, 4 or rinsing bath 9-12.
  • the workpieces 13 in the active bath 3, 4 are each connected to the negative pole 15, 16 of a controllable current source 17, 18 via the carrying device 14.
  • a metering device for the salt is present on each active bath 3, 4.
  • a metering device consists of a reservoir 23, 24 for a highly concentrated salt solution 25, 26, a suction line 27, 28, a metering pump 29, 30, a connecting line 31, 32, a controllable metering valve 33, 34 and an outlet 35, 36.
  • each rinsing bath 9-12 is also provided with metering devices, each rinsing bath 9-12 from a reservoir 37-40 for non-contaminated rinsing bath liquid 41-44, a suction line 45-48, a metering pump 49-52, a connecting line 53-56, a metering valve 57-60 and an outlet 61- 64 exist.
  • a device 65 for laser-induced spectral analysis is provided for monitoring the concentration of the coating metals in the active baths 3, 4 and the degree of contamination of foreign ions in the active baths 3, 4 and in the rinsing baths 9-12.
  • the device 65 contains a sample plate 66 with concentrically arranged sample wells 67.
  • the sample plate 66 is arranged to be rotatable about its central axis 68 by means of a stepping motor 69.
  • the device 65 is connected to the active baths 3, 4 and the rinsing baths 9-12 via a pipeline system.
  • the piping system includes a suction line 70-75, a pump 76-81, a connecting line 82-87, a controllable valve 88-93, and outlet lines 94-99, each for a sample well, for each active bath 3, 4 or rinsing bath 9-12 67 lead.
  • the device 65 further comprises a laser 100, the beam 101 of which is directed onto the pitch circle 102 of the sample wells 67 on the Sample plate 66 has.
  • the device 65 also includes a spectroscope 103 with an imaging system 104 and a radiation receiver 105.
  • the device 65 is assigned a cleaning device for the sample wells 67.
  • the cleaning device consists of a suction line 106, which starts from the pitch circle 102, a suction pump 107 and a line 108, which leads to a waste container 109.
  • a control and regulating device 110 is provided, which can be part of a control center of the electroplating system.
  • the control and regulating device 110 comprises a computer 111.
  • the computer 111 consists of a central processor 112, which is connected via a bus system 113 to a hard disk drive 114, an optional access memory 115, and read-only memory 116.
  • a keyboard 117 and a screen 118 are connected to the bus system 113.
  • the central processor 112 is used for timing and checking all elements connected to the bus system 113.
  • the random access memory 115 is used to store temporary instructions or data.
  • Read-only memory 116 contains unchangeable instructions, data, and programs that are necessary for the correct functioning of computer 111.
  • the hard disk drive 114 is a large-capacity memory for storing programs and data for the execution of the measured value processing and the calculation of manipulated variables.
  • the keyboard 117 enables data entry by an operator.
  • the screen 118 is used for outputting data and instructions to the operator.
  • the metering valves 33, 34, 57-60, the valves 88-93, the current sources 17, 18 are the measuring and control lines 119 shown in dashed lines and with suitable interfaces Suction pump 107, the stepper motor 69, the laser 100 and the spectroscope 103 are connected to the bus system 113.
  • the process can be carried out as follows:
  • the workpieces 13 are successively transported through the active bath 3, the rinsing baths 9, 11, the active bath 4 and the rinsing baths 10, 12 by means of the carrying devices 14 and said conveying devices.
  • the galvanic salt solutions become poor in ions of the coating metal.
  • the rinsing solutions are contaminated with foreign ions.
  • the method according to the invention is based on the fact that the device 65 continuously measures the concentrations of the coating metal ions in the active baths 3, 4 and the degrees of contamination of the active baths 3, 4 and the rinsing baths 9-12 with foreign ions.
  • small quantities of the active baths 3, 4 and rinsing baths 9-12 are each brought into one of the sample wells 67 through the connecting lines 82-87, the valves 88-93 and the outlet lines 94-99 by means of the pumps 76-81.
  • the control and regulating device 110 briefly opens one of the valves 88-93, so that, according to the program specified by the computer 111, samples one or more active baths 3, 4 or rinsing baths 9-12 are provided on the sample plate 66 for measurement with the device 65 become.
  • the stepper motor 69 causes the sample plate 66 to rotate about the central axis 68, so that a sample well 67 with a sample arrives in the direction of the beam 101 or the optical axis of the measuring beam path of the spectroscope 103.
  • the laser beam 101 excites the sample in a short time in such a way that it emits light, which for spectral analysis passes through the optical system 104 onto the radiation receiver 105.
  • the spectrum of the light at the radiation receiver 105 is characteristic of the elements contained in a sample and their concentrations.
  • the measured values of the spectroscope 103 are fed to the computer 111 and processed there.
  • control commands are issued to the metering valves 33, 34 via the bus system 113, so that the metering valves 33, 34 open for specific periods of time. While a metering valve 33, 34 opens, concentrated salt solution 25, 26 is supplied with the metering pumps 29, 30 for refreshment in the respective active bath 3, 4. The concentrated salt solution 25, 26 mixes with the depleted active bath solution, so that the concentration of the coating metal ions is kept essentially constant except for small control deviations.
  • the time course of the growth of a coating on the workpieces 13 can be influenced by adjusting the current flow in the active baths. For this purpose, control signals are sent from the control and regulating device 110 to the current sources 17, 18.
  • opening commands are sent from the control and regulating device 110 to the metering valves 57-60.
  • the metering valves 57-60 are opened for a certain period of time, fresh rinsing solution is supplied to the respective rinsing bath 9-12, while used rinsing solution is removed.
  • the sample plate 66 After analyzing a sample in a sample well 67, the sample plate 66 is rotated further with the stepper motor 69, so that the relevant sample well 67 reaches the location of the suction line 106.
  • the suction pump 107 receives an activation signal via the bus system 113, which activates the suction pump 107 and thus removes the rest of the sample from the sample well 67 into the waste container 109.
  • the device according to the invention is not limited to the exemplary embodiment shown.
  • the equipment of the piping system with pumps 76-81 and valves 88-93 is only an example.
  • the device 65 can be equipped with other devices for sample handling. Instead of the suction pump 107 and the suction line 106, other suitable cleaning devices for sample containers can be provided.
  • the means for refreshing the active baths 3, 4 and for regenerating the rinsing baths 9-12 can be designed differently than described.
  • the number of active baths 3, 4 and rinsing baths 9-12 can be adapted to the respective requirements. List of the reference symbols used

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Automation & Control Theory (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
  • Investigating Or Analysing Materials By Optical Means (AREA)

Abstract

L'invention concerne un procédé et un dispositif pour réguler au moins une grandeur d'exploitation d'un bain électrolytique. L'objectif de l'invention est de développer un procédé et un dispositif permettant la réalisation de revêtements d'une meilleure qualité, respectivement selon lequel et avec lequel l'utilisation de produits chimiques est réduite. Selon ledit procédé, la concentration d'au moins un composant du bain est déterminée, les valeurs de concentration sont en outre traitées dans un dispositif de commande pour être transformées en grandeurs de réglage d'un organe de réglage, et la grandeur d'exploitation est modifiée avec l'organe de réglage conformément à la valeur de consigne. L'invention réside dans le fait que la concentration est déterminée au moyen d'un échantillon prélevé dans le bain (3, 4, 9-12) qui est excité au moyen d'un rayonnement électromagnétique (101), le spectre de la lumière émise par ledit échantillon étant analysé. Ce dispositif comprend un système (70-75, 82-87, 94-99) servant au transfert d'au moins un échantillon d'un bain (3, 4, 9-12) à un dispositif (65) utilisé pour déterminer la concentration. Ce dispositif (65), qui sert à la détermination de la concentration d'au moins un composant du bain, contient un laser (100) qui est dirigé vers l'échantillon et il comprend un dispositif (103) pour l'analyse du spectre de la lumière émise par l'échantillon.
EP04723967A 2003-03-29 2004-03-29 Procede et dispositif pour reguler au moins une grandeur d'exploitation d'un bain electrolytique Withdrawn EP1611270A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10314279A DE10314279A1 (de) 2003-03-29 2003-03-29 Verfahren und Vorrichtung zum Steuern mindestens einer Betriebsgröße eines elektrolytischen Bades
PCT/DE2004/000653 WO2004088003A2 (fr) 2003-03-29 2004-03-29 Procede et dispositif pour reguler au moins une grandeur d'exploitation d'un bain electrolytique

Publications (1)

Publication Number Publication Date
EP1611270A2 true EP1611270A2 (fr) 2006-01-04

Family

ID=32980796

Family Applications (1)

Application Number Title Priority Date Filing Date
EP04723967A Withdrawn EP1611270A2 (fr) 2003-03-29 2004-03-29 Procede et dispositif pour reguler au moins une grandeur d'exploitation d'un bain electrolytique

Country Status (4)

Country Link
US (1) US20060246591A1 (fr)
EP (1) EP1611270A2 (fr)
DE (1) DE10314279A1 (fr)
WO (1) WO2004088003A2 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015002942A1 (fr) * 2013-07-03 2015-01-08 Tel Nexx, Inc. Appareil de dépôt électrochimique et procédés de contrôle de la chimie à l'intérieur de ce dernier
CN117721513B (zh) * 2024-02-18 2024-04-16 深圳市海里表面技术处理有限公司 基于光谱分析的自适应镀银方法及系统

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US4326940A (en) * 1979-05-21 1982-04-27 Rohco Incorporated Automatic analyzer and control system for electroplating baths
JPS61241639A (ja) * 1985-04-19 1986-10-27 Hitachi Ltd 反応試料分析装置
DE4405741C1 (de) * 1994-02-23 1995-06-01 Atotech Deutschland Gmbh Verfahren zur elektrolytischen Abscheidung von Metallen aus Elektrolyten mit Prozeßorganik
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Also Published As

Publication number Publication date
US20060246591A1 (en) 2006-11-02
WO2004088003A2 (fr) 2004-10-14
WO2004088003A3 (fr) 2004-12-09
DE10314279A1 (de) 2004-10-14

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