EP0722515B1 - Process for the galvanic application of a surface coating - Google Patents

Process for the galvanic application of a surface coating Download PDF

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Publication number
EP0722515B1
EP0722515B1 EP94928407A EP94928407A EP0722515B1 EP 0722515 B1 EP0722515 B1 EP 0722515B1 EP 94928407 A EP94928407 A EP 94928407A EP 94928407 A EP94928407 A EP 94928407A EP 0722515 B1 EP0722515 B1 EP 0722515B1
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Prior art keywords
current
current density
process according
stages
seconds
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EP94928407A
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German (de)
French (fr)
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EP0722515A1 (en
Inventor
Karl Müll
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Winterthurer Metallveredelung AG
Heidelberger Druckmaschinen AG
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Winterthurer Metallveredelung AG
Heidelberger Druckmaschinen AG
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Priority claimed from DE4334122A external-priority patent/DE4334122C2/en
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/625—Discontinuous layers, e.g. microcracked layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B17/00—Methods preventing fouling
    • B08B17/02—Preventing deposition of fouling or of dust
    • B08B17/06—Preventing deposition of fouling or of dust by giving articles subject to fouling a special shape or arrangement
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B17/00—Methods preventing fouling
    • B08B17/02—Preventing deposition of fouling or of dust
    • B08B17/06—Preventing deposition of fouling or of dust by giving articles subject to fouling a special shape or arrangement
    • B08B17/065—Preventing deposition of fouling or of dust by giving articles subject to fouling a special shape or arrangement the surface having a microscopic surface pattern to achieve the same effect as a lotus flower
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/18—Electroplating using modulated, pulsed or reversing current
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance

Definitions

  • the invention relates to a method for electrochemical (galvanic) application of a surface coating according to the German application with the file number DE 42 11 881.6-24.
  • Such surface structures are created by chemical Etching processes after the coating or through mechanical processing methods such as grinding or Sandblasting more or less well achieved. To that The created surface structure then becomes a Hard chrome layer applied.
  • mechanical processing methods such as grinding or Sandblasting more or less well achieved.
  • the created surface structure then becomes a Hard chrome layer applied.
  • Dispersion deposition processes used in which a specific surface structure through organic or inorganic foreign substances is achieved, for example be built into a chrome layer and / or growth block the chrome layer during the deposition process, so that rough surfaces arise.
  • the foreign substances are present as dispersants in the electrolyte.
  • DE 33 07 748 relates to a method for electrochemical Coating in which a pulsed current is used for nucleation is used. If an appropriate current density is used the resulting germs form a dendritic Structure. This allows rough, Generate dendritic structured surfaces. Under the Current density becomes the average current density at the Understand the cathode surface.
  • the invention has for its object an improved Process for the electrochemical application of Structural metal layers based on mechanical or chemical Post-treatments are dispensed with and with the varied Structural metal layers can be generated, as well as a To provide an apparatus for performing this method.
  • the structure layer is directly galvanically towards the coated object applied. This must be a have an electrically conductive surface, as a rule is sanded around a smooth base for the structural layer to offer.
  • the object Before the coating process, the object is after usual galvanotechnical rules cleaned and degreased. It is immersed as a cathode in a galvanic bath which also has an anode. The distance between the anode and cathode is usually in the range between 1 and 40 cm chosen.
  • Chromium electrolytes are preferred as electrolyte, especially sulfuric acid, chromium electrolytes, mixed acid Chromium electrolytes or alloy electrolytes are used.
  • a process voltage can be applied between the anode and the cathode and the flowing current causes an application of material to the object to be coated, which is used as the cathode.
  • the invention proposes applying positive current jumps to form germs.
  • the structure creation process consists of a nucleation phase and a germ growth phase.
  • the process voltage and process current are increased in several stages, each with a predeterminable change in the current density from 1 to 6 mA / cm 2 per stage, from an initial value to a structure current density.
  • the initial value is 0 mA / cm 2 , but this can also be higher if the nucleation phase immediately follows a previous galvanic process phase and the current in between is not reduced to zero.
  • the time between two current density increases is 0.1 to 30 seconds. step spacings of about 7 seconds are most commonly used. With each jump in current, new germs are formed. In contrast to pulse current coating, the process current does not go back to zero after every positive jump, but is increased further with every current jump. In this way, in particular round and more uniformly shaped germs or bodies can be deposited on the object than is possible with the known pulse current methods.
  • the current stages are applied to the bath in such a number until a structural layer consisting of a precipitate of individual or stacked, approximately spherical or dendritic bodies is reached on the surface of the object.
  • the nucleation phase Structural layer thickness of 4 ⁇ m to 10 ⁇ m is aimed for. To do this usually between 10 and 240 current steps necessary, particularly good results are achieved with 50 to 60 levels reached.
  • the reached after completion of the last current stage Current density is the structure current density.
  • current density is the nucleation phase that actual formation of the structure, largely completed.
  • the structure of the emerging structure is many Parameters, especially the selected structure current density, on the number, the amount and the time interval of the Current levels, the bath temperature and the used Depends on electrolytes.
  • Character of the current function can be different Surface structures are generated, the main thing are characterized by different roughness depths.
  • the ideal process parameters can simply be empirical be determined. As a rule, it can be said that at higher bath temperature and higher acidity of the Electrolytes also used a larger structure current density becomes.
  • This structure current density is usually two to three times the current density used in normal DC coating.
  • DC coating current densities in the range from 15 to 60 mA / cm 2 are used .
  • the value of the current density depends on the electrolyte and the bath temperature.
  • Current densities in the range from 30 to 180 mA / cm 2 are possible for structure coating.
  • the germ growth phase It is during a Predeterminable ramp working time with a process stream Current density in the range of 80% to 120% of the Structure current density created. During ramp work hours an approximately even current flows, which leads to growth the structure created on the object. Depending on the duration of the Ramp working time can do this structural layer more or be less pronounced. The growth takes place doing it faster at the highest points of the structure layer than at the lows between those in the nucleation phase bulky bodies. This initially results in one further increase in roughness during the germ growth phase.
  • the ramp working time is usually in a range from 1 to 600 seconds, preferably around 30 seconds.
  • the current levels are preferably in a range from -1 to -8 mA / cm 2 per level and the time between two current levels is preferably selected in the range from 0.1 to 1 second.
  • the object to be coated already becomes a few Time, preferably one minute before the start of the process in the bath immersed.
  • This waiting time mainly serves the Temperature adjustment, that is, the base material takes about the temperature of the electrolyte.
  • the device for carrying out the described method consists of a galvanic bath which contains an electrolytic bath solution containing a metal concentration.
  • Chromium electrolytes are preferred as the electrolyte, in particular sulfuric acid chromium electrolytes, mixed acid chromium electrolytes or alloy electrolytes.
  • a preferred electrolyte has a concentration of 180 to 300 grams of chromic acid CrO 3 per liter.
  • third-party additives such.
  • B. sulfuric acid H 2 SO 4 , hydrofluoric acid H 2 F 2 , silica hydrofluoric acid H 2 SiF 6 and mixtures thereof are added.
  • a preferred electrolyte contains 1 to 3.5 grams of sulfuric acid H 2 SO 4 per liter.
  • the galvanic bath is usually heated, the temperature of the electrolyte is preferably 30 to 55 degrees Celsius.
  • An anode and a cathode are immersed in the electrolytic bath solution, the object to be coated forming the cathode or being at least part of the cathode. If a chrome electrolyte is used, platinum-plated platinum or PbSn7 are preferably used as the anode material.
  • Anode and cathode are connected to a device for feeding a process current.
  • the process current can be increased from the initial value to the structure current density in several stages, each with a predeterminable change in the current density of 1 to 6 mA / cm 2 per stage.
  • the time intervals between two current increases can be set between 0.1 and 30 seconds.
  • a process current with a current density in the range of 80% to 120% of the structure current density can be applied for a predeterminable ramp working time.
  • the device can be equipped with a rotary drive for continuously rotating the object.
  • the distance between the anode and the object to be coated is selected in the range from 1 to 40 cm, preferably at 25 cm.
  • Fig. 1 shows the schematic representation of a device for the galvanic application of structural layers.
  • In the galvanic bath is a too coating object 2 and an anode 3 immersed. That too Coating object forms the cathode 2.
  • Anode and cathode are with a controlled electrical energy source 4th connected.
  • the energy source can be an electricity or be a voltage source.
  • the current respectively the Current density at the cathode is decisive for the coating is the process can be more accurate with a power source check.
  • the use of a voltage source has in contrast, the advantage of a lower electrical Circuit effort.
  • the bath temperature and the concentration of the electrolyte are not The process can also be significantly changed with a Check the voltage source well.
  • the electrical energy source 4 is from a programmable control unit 5 controlled.
  • the Control unit can be any time voltage, or specify current curves, which are then automatically via Energy source 4 are placed on the electrodes.
  • Fig. 2 shows the graphical representation of the temporal Process current density curve when generating a Structural layer.
  • 2 is the horizontal axis Time axis, on the vertical axis y is the current density shown. This is an exemplary embodiment for a possible procedure that follows is described in more detail.
  • Figures 3 and 4 show photographic representations of using this process generated structure layer.
  • a sulfuric acid chromium electrolyte with 200 grams of chromic acid CrO 3 and 2 grams of sulfuric acid H 2 SO 4 is used as the galvanic bath.
  • the workpiece to be coated is a rotationally symmetrical component, a dampening cylinder for the printing industry.
  • the cylinder consisting of St52 is first finely ground, with a roughness depth of Rz ⁇ 3 ⁇ m.
  • a 30 ⁇ m thick nickel layer and then a 10 ⁇ m thick, crack-free chrome layer are then applied according to the conditions customary in electroplating.
  • the workpiece prepared in this way is rotated for structural chrome plating in the galvanic bath in order to achieve a coating that is as uniform as possible.
  • the workpiece forms the cathode, platinum-plated titanium or PbSn7 is used as the anode.
  • the anode / cathode electrode spacing is set to 25 cm.
  • the process stream remains switched off during a first process phase 7.
  • This phase serves to acclimatize the workpiece to the galvanic bath.
  • the workpiece takes on the temperature of the electrolyte.
  • a direct current between the anode and cathode is switched on. This remains switched on during phase 8, which lasts about 600 seconds.
  • a chrome-G DC base layer is applied to the workpiece.
  • the current density used is also common for normal chrome plating, here 20 mA / cm 2 .
  • a second phase 9 follows without current.
  • the current density is increased in steps to the structure current density 14.
  • the characteristic data of the stages are varied during the ascent.
  • the current is increased in 16 steps to 40 mA / cm 2 . This corresponds to a change in the current density of 2.5 mA / cm 2 per stage.
  • the time 28 between two current stages is 5 seconds.
  • the current density during phase 11 is then increased in 62 further steps to the structure current density of 100 mA / cm 2 , the time between two current stages is 6 seconds (the current density curve shown in the graph in FIG. 2 is not to scale, the same applies to that in FIG 5 and 6 graphs).
  • this current density is maintained during the ramp working time 12.
  • the direct current flowing thereby leads to the growth of the structural layer produced in phases 10 and 11.
  • the ramp work time is 60 seconds.
  • the current density is again gradually reduced in 22 steps to the final value of 0 mA / cm 2 .
  • the time between two current steps is 4 seconds.
  • Chromium structure layer still a 4 to 8 ⁇ m thick micro-cracked Chrome layer applied. This happens among those in the Electroplating common DC conditions and will be here not explained in more detail.
  • FIG. 3 and 4 show microscopic images of the Chromium structural layer according to that described in FIG. 2 Process was generated.
  • the structure layer exists predominantly of spherical, individual and partial also bodies lying against each other.
  • the "load share” is also as "Material proportion" defined in accordance with DIN 4762.
  • FIG. 5 shows the current density profile over time of a further process sequence for the coating of structures.
  • the process phases 7, 8 and 9 have already been discussed in the explanations for FIG. 2.
  • the current density is increased in 110 identical steps to the structure current density of 100 mA / cm 2 .
  • the time between two current steps is 10 seconds.
  • the current density is reduced, this time in 22 identical steps, to the final value of O mA / cm 2 .
  • the time between two current steps is 4 seconds. Following this, after a brief current-free moment, the process cycle consisting of phases 15, 16 and 17 is repeated.
  • FIG. 6 shows the temporal current density profile of a further method profile.
  • a direct current pulse 18 which corresponds in its nature to the direct current pulse 8 in FIG. 2.
  • a nucleation phase 19 in which the current density is gradually increased to the structure current density 24.
  • the current density is then kept at the structure current density during the ramp working time 20 and is then ramped down to an end value 26 during the phase 21.
  • a nucleation phase 23 with a gradual increase in the current density up to the new structure current density 25.
  • the initial current density of the nucleation phase 23 is equal to the end value 26 to which the current density was reduced at the end of the previous structure generation cycle.
  • the current density is then kept at the structure current density 25 during the ramp working time 27 and subsequently abruptly reduced to the new final value of 0 mA / cm 2 .

Abstract

The invention relates to a galvanic coating process to provide a structured surface coating on a workpiece with an electrically conductive surface and a device for implementing the process. Here, the object to be coated is the cathode in a galvanic bath. The process current is raised in steps during a nucleation phase (10, 11) in which the stepwise increase in the current results in the formation of a deposit of individual or adjacent bodies on the surface of the object. The process current is then kept constant during a ramp working period (12), resulting in the growth of the previously produced nuclei or bodies. The process may be cyclically repeated.

Description

Die Erfindung betrifft ein Verfahren zum elektrochemischen (galvanischen) Aufbringen einer Oberflächenbeschichtung gemäß der deutschen Anmeldung mit dem Aktenzeichen DE 42 11 881.6-24.The invention relates to a method for electrochemical (galvanic) application of a surface coating according to the German application with the file number DE 42 11 881.6-24.

Solche Oberflächenstrukturen werden durch chemische Ätzprozesse im Anschluß an die Beschichtung oder durch mechanische Bearbeitungsverfahren wie etwa Schleifen oder Sandstrahlen mehr oder weniger gut erreicht. Auf die so geschaffene Oberflächenstruktur wird dann eine Hartchromschicht aufgebracht. Diese verschiedenen, zur Erstellung notwendigen Arbeitsschritte sind aufwendig und erfordern eine komplizierte Verfahrenstechnik. Die Kosten werden im Wesentlichen durch die mechanischen oder chemischen Bearbeitungsschritte zur Strukturerzeugung bestimmt.Such surface structures are created by chemical Etching processes after the coating or through mechanical processing methods such as grinding or Sandblasting more or less well achieved. To that The created surface structure then becomes a Hard chrome layer applied. These different, for Creation of necessary work steps are complex and require complicated process engineering. The costs are essentially mechanical or chemical Processing steps for structure generation determined.

Im Bereich der Strukturierung von Metallschichten werden auch aufwendige und nur sehr schwer beherrschbare Dispersionsabscheideverfahren eingesetzt, bei denen eine spezifische Oberflächenstruktur durch organische oder anorganische Fremdsubstanzen erzielt wird, die zum Beispiel in einer Chromschicht eingebaut werden und/oder das Wachstum der Chromschicht während des Abscheidevorganges blockieren, so daß rauhe Oberflächen entstehen. Die Fremdsubstanzen liegen als Dispergat im Elektrolyt vor.In the field of structuring metal layers, too complex and very difficult to control Dispersion deposition processes used in which a specific surface structure through organic or inorganic foreign substances is achieved, for example be built into a chrome layer and / or growth block the chrome layer during the deposition process, so that rough surfaces arise. The foreign substances are present as dispersants in the electrolyte.

Die DE 33 07 748 betrifft ein Verfahren zur elektrochemischen Beschichtung, bei dem zur Keimbildung ein pulsförmiger Strom verwendet wird. Wenn eine geeignete Stromdichte verwendet wird, bilden die entstehenden Keime eine dendritische Struktur. Damit lassen sich in einem Arbeitsgang rauhe, dendritisch strukturierte Oberflächen erzeugen. Unter der Stromdichte wird die mittlere Stromdichte an der Kathodenoberfläche verstanden. DE 33 07 748 relates to a method for electrochemical Coating in which a pulsed current is used for nucleation is used. If an appropriate current density is used the resulting germs form a dendritic Structure. This allows rough, Generate dendritic structured surfaces. Under the Current density becomes the average current density at the Understand the cathode surface.

Der Erfindung liegt die Aufgabe zugrunde, ein verbessertes Verfahren zum elektrochemischen Aufbringen von Strukturmetallschichten, das auf mechanische oder chemische Nachbehandlungen verzichtet und mit dem vielfältige Strukturmetallschichten erzeugbar sind, sowie eine Vorrichtung zum Durchführen dieses Verfahrens zu schaffen.The invention has for its object an improved Process for the electrochemical application of Structural metal layers based on mechanical or chemical Post-treatments are dispensed with and with the varied Structural metal layers can be generated, as well as a To provide an apparatus for performing this method.

Erfindungsgemäß wird diese Aufgabe gemäß den Merkmalen der Kennzeichen der Patentansprüche gelöst.According to the invention, this object is achieved according to the features of Characteristic of the claims solved.

Die Strukturschicht wird direkt galvanisch auf das zu beschichtende Objekt aufgetragen. Dieses muß dazu eine elektrisch leitfähige Oberfläche aufweisen, die in der Regel geschliffen ist um eine glatte Basis für die Strukturschicht zu bieten. Vor dem Beschichtungsprozeß wird das Objekt nach üblichen galvanotechnischen Regeln gereinigt und entfettet. Es ist als Kathode in ein galvanisches Bad eingetaucht, in dem sich auch eine Anode befindet. Der Abstand zwischen Anode und Kathode wird meist im Bereich zwischen 1 und 40 cm gewählt. Als Elektrolyt werden bevorzugt Chromelektrolyte, insbesondere Schwefelsaure Chromelektrolyte, Mischsaure Chromelektrolyte oder Legierungselektrolyte verwendet.The structure layer is directly galvanically towards the coated object applied. This must be a have an electrically conductive surface, as a rule is sanded around a smooth base for the structural layer to offer. Before the coating process, the object is after usual galvanotechnical rules cleaned and degreased. It is immersed as a cathode in a galvanic bath which also has an anode. The distance between the anode and cathode is usually in the range between 1 and 40 cm chosen. Chromium electrolytes are preferred as electrolyte, especially sulfuric acid, chromium electrolytes, mixed acid Chromium electrolytes or alloy electrolytes are used.

Zwischen Anode und Kathode kann eine Prozeßspannung angelegt werden und der fließende Strom bewirkt einen Materialauftrag an dem als Kathode benutzten, zu beschichtenden Objekt. Die Erfindung schlägt vor, zur Bildung von Keimen positive Stromsprünge anzulegen. Der Prozeß der Strukturerzeugung besteht aus einer Keimbildungsphase und einer Keimwachstumsphase. Zunächst werden in der Keimbildungsphase Prozeßspannung und Prozeßstrom in mehreren Stufen mit jeweils einer vorbestimmbaren Änderung der Stromdichte von 1 bis 6 mA/cm2 pro Stufe von einem Anfangswert auf eine Strukturstromdichte erhöht. Der Anfangswert beträgt 0 mA/cm2, der kann jedoch auch höher sein, wenn die Keimbildungsphase direkt auf eine vorhergehende galvanische Prozeßphase folgt und der Strom dazwischen nicht auf Null abgesenkt wird. Die Zeit zwischen zwei Stromdichte-Erhöhungen beträgt 0,1 bis 30 Sekunden. am häufigsten werden Stufenabstände von etwa 7 Sekunden verwendet. Mit jedem Stromsprung werden neue Keime gebildet. Im Gegensatz zum Pulsstrom-Beschichten geht hier der Prozeßstrom nicht nach jedem positiven Sprung wieder auf Null zurück sondern er wird mit jedem Stromsprung weiter erhöht. Damit können insbesondere runder und gleichmäßiger geformte Keime, bzw. Körper auf dem Objekt abgeschieden werden, als dies mit den bekannten Pulsstrom-Verfahren möglich ist. Die Stromstufen werden in einer solchen Anzahl an das Bad gelegt, bis eine Strukturschicht bestehend aus einem Niederschlag aus einzelnen oder aneinandergelagerten, etwa kugelförmigen oder dendritischen Körpern auf der Oberfläche des Objekts erreicht ist.A process voltage can be applied between the anode and the cathode and the flowing current causes an application of material to the object to be coated, which is used as the cathode. The invention proposes applying positive current jumps to form germs. The structure creation process consists of a nucleation phase and a germ growth phase. First, in the nucleation phase, the process voltage and process current are increased in several stages, each with a predeterminable change in the current density from 1 to 6 mA / cm 2 per stage, from an initial value to a structure current density. The initial value is 0 mA / cm 2 , but this can also be higher if the nucleation phase immediately follows a previous galvanic process phase and the current in between is not reduced to zero. The time between two current density increases is 0.1 to 30 seconds. step spacings of about 7 seconds are most commonly used. With each jump in current, new germs are formed. In contrast to pulse current coating, the process current does not go back to zero after every positive jump, but is increased further with every current jump. In this way, in particular round and more uniformly shaped germs or bodies can be deposited on the object than is possible with the known pulse current methods. The current stages are applied to the bath in such a number until a structural layer consisting of a precipitate of individual or stacked, approximately spherical or dendritic bodies is reached on the surface of the object.

Vorzugsweise wird mit der Keimbildungsphase eine Strukturschichtdicke von 4 µm bis 10 µm angestrebt. Dazu sind in der Regel zwischen 10 und 240 Stromstufen notwendig, besonders gute Ergebnisse werden mit 50 bis 60 Stufen erreicht.Preferably, with the nucleation phase Structural layer thickness of 4 µm to 10 µm is aimed for. To do this usually between 10 and 240 current steps necessary, particularly good results are achieved with 50 to 60 levels reached.

Die nach Abschluß der letzten Stromstufe erreichte Stromdichte ist die Strukturstromdichte. Mit dem Erreichen dieser Strukturstromdichte ist die Keimbildungsphase, die eigentliche Bildung der Struktur, weitgehend abgeschlossen. Der Aufbau der entstehenden Struktur ist von vielen Parametern, vor allem von der gewählten Strukturstromdichte, von der Anzahl, der Höhe und dem zeitlichen Abstand der Stromstufen, von der Badtemperatur und von dem verwendeten Elektrolyten abhängig. Die Änderung der Stromdichte pro Stufe wie auch die Zeit zwischen zwei Stromdichte-Erhöhungen kann während der Keimbildungsphase verändert werden. Je nach Charakter der Stromfunktion können unterschiedliche Oberflächenstrukturen erzeugt werden, die in der Hauptsache durch unterschiedliche Rauhtiefen gekennzeichnet sind. Die idealen Verfahrensparameter können einfach empirisch festgestellt werden. In der Regel läßt sich sagen, daß bei höherer Badtemperatur und höherem Säuregehalt des Elektrolyten auch eine größere Strukturstromdichte verwendet wird.The reached after completion of the last current stage Current density is the structure current density. With reaching this structure current density is the nucleation phase that actual formation of the structure, largely completed. The structure of the emerging structure is many Parameters, especially the selected structure current density, on the number, the amount and the time interval of the Current levels, the bath temperature and the used Depends on electrolytes. The change in current density per stage as can the time between two current density increases be changed during the nucleation phase. Depending on Character of the current function can be different Surface structures are generated, the main thing are characterized by different roughness depths. The ideal process parameters can simply be empirical be determined. As a rule, it can be said that at higher bath temperature and higher acidity of the Electrolytes also used a larger structure current density becomes.

Diese Strukturstromdichte beträgt in der Regel das Zwei- bis Dreifache der bei normalem Gleichstrombeschichten verwendeten Stromdichte. Beim Gleichstrombeschichten wird mit Stromdichten im Bereich von 15 bis 60 mA/cm2 gearbeitet. Der Wert der Stromdichte ist dabei vom Elektrolyt und der Badtemperatur abhängig. Beim Strukturbeschichten sind Stromdichten im Bereich von 30 bis 180 mA/cm2 möglich.This structure current density is usually two to three times the current density used in normal DC coating. With DC coating, current densities in the range from 15 to 60 mA / cm 2 are used . The value of the current density depends on the electrolyte and the bath temperature. Current densities in the range from 30 to 180 mA / cm 2 are possible for structure coating.

Danach folgt die Keimwachstumsphase. Dabei wird während einer vorbestimmbaren Rampenarbeitszeit ein Prozeßstrom mit einer Stromdichte im Bereich von 80% bis 120% der Strukturstromdichte angelegt. Während der Rampenarbeitszeit fließt ein etwa gleichmäßiger Strom, dies führt zum Wachstum der auf dem Objekt erzeugten Struktur. Je nach Dauer der Rampenarbeitszeit kann diese Strukturschicht mehr oder weniger stark ausgeprägt werden. Das Wachstum vollzieht sich dabei an den höchsten Punkten der Strukturschicht schneller als an den Tiefpunkten zwischen den in der Keimbildungsphase auftragenden Körpern. Dadurch ergibt sich zunächst eine weitere Zunahme der Rauheit während der Keimwachstumsphase. Die Rampenarbeitszeit liegt meist in einem Bereich von 1 bis 600 Sekunden, vorzugsweise bei etwa 30 Sekunden.This is followed by the germ growth phase. It is during a Predeterminable ramp working time with a process stream Current density in the range of 80% to 120% of the Structure current density created. During ramp work hours an approximately even current flows, which leads to growth the structure created on the object. Depending on the duration of the Ramp working time can do this structural layer more or be less pronounced. The growth takes place doing it faster at the highest points of the structure layer than at the lows between those in the nucleation phase bulky bodies. This initially results in one further increase in roughness during the germ growth phase. The ramp working time is usually in a range from 1 to 600 seconds, preferably around 30 seconds.

Nach Ablauf der Rampenarbeitszeit wird der Prozeßstrom auf einen Endwert, häufig auf Null, abgesenkt. Dieses Absenken des Prozeßstroms auf den Endwert kann sprungartig geschehen, es ist jedoch auch ein rampenförmiges Absenken möglich. Auch hier wurden mit stufenweiser Änderung des Prozeßstroms gute Resultate erzielt. Die Stromstufen liegen dabei vorzugsweise in einem Bereich von -1 bis -8 mA/cm2 pro Stufe und die Zeit zwischen zwei Stromstufen wird vorzugsweise im Bereich von 0,1 bis 1 Sekunde gewählt.After the ramp working time has expired, the process current is reduced to a final value, often to zero. This lowering of the process stream to the final value can occur suddenly, but a ramp-shaped lowering is also possible. Here too, good results were achieved with a gradual change in the process stream. The current levels are preferably in a range from -1 to -8 mA / cm 2 per level and the time between two current levels is preferably selected in the range from 0.1 to 1 second.

Vorstehend wurden drei Verfahrensschritte beschrieben: Das stufenweise Erhöhen des Prozeßstroms während der Keimbildungsphase bis zum Erreichen der Strukturstromdichte, das Halten des Prozeßstroms im Bereich der Strukturstromdichte während der Rampenarbeitszeit (Keimwachstumsphase) und das anschließende Absenken des Prozeßstroms auf einen Endwert. Diese Verfahrensschritte stellen einen Strukturerzeugungs-Zyklus dar. Sie können zyklisch wiederholt werden. Dies ist insbesondere dann von Vorteil, wenn eine stärkere Strukturierung der Oberfläche gewünscht ist. Dabei entspricht jeweils der Endwert des vorhergehenden Zyklus dem Anfangswert des folgenden Zyklus. Die Anzahl der Wiederholungen ist von der gewünschten Oberflächenstruktur und Schichtdicke abhängig. Gute Resultate wurden mit Wiederholungen zwischen zweimal und zwanzigmal erreicht. Die Endwerte der einzelnen Zyklen können unterschiedlich hoch sein.Three process steps have been described above: The gradually increasing the process stream during the Nucleation phase until the structure current density is reached, keeping the process stream in the range of Structure current density during ramp working hours (Germ growth phase) and the subsequent lowering of the Process stream to a final value. These process steps represent a structure creation cycle. You can be repeated cyclically. This is especially true of Advantage if a stronger structuring of the surface is desired. The end value of each corresponds previous cycle the initial value of the following cycle. The number of repetitions is the desired number Surface structure and layer thickness dependent. Good results were done with repetitions between two and twenty times reached. The end values of the individual cycles can be different heights.

Mit Vorteil wird das zu beschichtende Objekt bereits einige Zeit, vorzugsweise eine Minute vor Prozeßbeginn in das Bad eingetaucht. Diese Wartezeit dient vor allem der Temperaturangleichung, das heißt, der Grundwerkstoff nimmt etwa die Temperatur des Elektrolyten an.Advantageously, the object to be coated already becomes a few Time, preferably one minute before the start of the process in the bath immersed. This waiting time mainly serves the Temperature adjustment, that is, the base material takes about the temperature of the electrolyte.

Gute Resultate werden erreicht, wenn vor dem Auftragen der Strukturschicht unter beim Normalverchromen üblichen Bedingungen eine Gleichstrom-Grundschicht aufgetragen wird. Dies wird dadurch erreicht, daß zu Beginn der Beschichtung ein Grundimpuls (Spannungs- bzw. Stromimpuls) angelegt wird. Dabei wird eine Stromdichte von 15 bis 60 mA/cm2 verwendet, was den beim Normalverchromen üblichen Stromwerten entspricht. Dieser Grundimpuls hat eine Dauer von etwa 600 Sekunden. Um Konzentrationsänderungen durch die vorgeschaltete Gleichstrombehandlung in der Phasengrenzschicht vor der Strukturerzeugung zu eliminieren ist es vorteilhaft, wenn nach dem Grundimpuls und vor Beginn der Strukturerzeugung eine stromfreie Zwischenzeit von etwa 60 Sekunden eingefügt wird.Good results are achieved if a DC base layer is applied before the application of the structural layer under the conditions customary for normal chrome plating. This is achieved by applying a basic pulse (voltage or current pulse) at the beginning of the coating. A current density of 15 to 60 mA / cm 2 is used, which corresponds to the current values usual for normal chrome plating. This basic pulse has a duration of approximately 600 seconds. In order to eliminate changes in concentration due to the upstream direct current treatment in the phase boundary layer before the structure is generated, it is advantageous to insert a current-free intermediate time of approximately 60 seconds after the basic pulse and before the structure is started.

Dieses Verfahren wird in vielen Bereichen der Technik für Bauteile mit speziellen Oberflächeneigenschaften benötigt. Es ist bekannt, Oberflächenbeschichtungen auf Bauteilen mittels galvanischer Prozesse aufzubringen. Häufig werden bestimmte Anforderungen an die Oberflächenstruktur des beschichteten Werkstücks gestellt. Zum Beispiel sollen Zylinderlaufflächen definierte Schmierstoffdepots zur Aufnahme von Schmiermitteln aufweisen und medizinische oder optische Geräte sollen Oberflächen mit niedrigem Reflexionsgrad aufweisen. Definierte Reflexionsgrade sind auch für funktionelle und dekorative Anwendungen in der Möbel- und Sanitär-Armaturen-Industrie gefordert. In der graphischen Industrie werden für Druckmaschinen Feuchtreibzylinder mit einer speziellen, "rauhen" Oberfläche benötigt. In der Umformtechnik können strukturverchromte Werkzeuge verwendet werden um dem Werkstück eine strukturierte Oberfläche zu geben. Zum Beispiel kann die Oberfläche von Blech durch Walzen mit strukturverchromten Rollen strukturiert werden.This process is used in many areas of technology Components with special surface properties are required. It is known to use surface coatings on components to apply galvanic processes. Certain are often Requirements for the surface structure of the coated Workpiece. For example, cylinder liners defined lubricant depots to hold lubricants have and should medical or optical devices Have surfaces with low reflectance. Defined reflectances are also for functional and decorative applications in furniture and Sanitary fittings industry required. In the graphic Industry are using dampening cylinders for printing presses a special, "rough" surface. In the Metal forming technology can use chromium-plated tools create a structured surface around the workpiece give. For example, the surface of sheet metal through Structured rollers with chrome-plated rollers.

Die Vorrichtung zur Durchführung des beschriebenen Verfahrens besteht aus einem galvanischen Bad, das eine eine Metallkonzentration enthaltende elektrolytische Badlösung enthält. Als Elektrolyt werden Chromelektrolyte bevorzugt, insbesondere Schwefelsaure Chromelektrolyte, Mischsaure Chromelektrolyte oder Legierungselektrolyte. Ein bevorzugter Elektrolyt weist eine Konzentration von 180 bis 300 Gramm Chromsäure CrO3 pro Liter auf. Dazu können Fremdzusätze wie z. B. Schwefelsäure H2SO4, Fluorwasserstoffsäure H2F2, Kieselfluorwasserstoffsäure H2SiF6 und deren Mischungen zugefügt werden. Ein bevorzugter Elektrolyt enthält 1 bis 3.5 Gramm Schwefelsäure H2SO4 pro Liter. Das galvanische Bad wird in der Regel beheizt, die Temperatur des Elektrolyts beträgt vorzugsweise 30 bis 55 Grad Celsius.The device for carrying out the described method consists of a galvanic bath which contains an electrolytic bath solution containing a metal concentration. Chromium electrolytes are preferred as the electrolyte, in particular sulfuric acid chromium electrolytes, mixed acid chromium electrolytes or alloy electrolytes. A preferred electrolyte has a concentration of 180 to 300 grams of chromic acid CrO 3 per liter. For this, third-party additives such. B. sulfuric acid H 2 SO 4 , hydrofluoric acid H 2 F 2 , silica hydrofluoric acid H 2 SiF 6 and mixtures thereof are added. A preferred electrolyte contains 1 to 3.5 grams of sulfuric acid H 2 SO 4 per liter. The galvanic bath is usually heated, the temperature of the electrolyte is preferably 30 to 55 degrees Celsius.

In die elektrolytische Badlösung sind eine Anode und eine Kathode eingetaucht, wobei das zu beschichtende Objekt die Kathode bildet oder zumindest Teil der Kathode ist. Bei Verwendung eines Chromelektrolyten werden bevorzugt platiniertes Platin oder PbSn7 als Anodenmaterial verwendet. Anode und Kathode sind mit einer Einrichtung zum Einspeisen eines Prozeßstroms verbunden. Der Prozeßstrom ist in mehreren Stufen mit jeweils einer vorbestimmbaren Änderung der Stromdichte von 1 bis 6mA/cm2 pro Stufe von dem Anfangswert auf die Strukturstromdichte erhöhbar. Die zeitlichen Abstände zwischen zwei Stromerhöhungen sind zwischen 0,1 und 30 Sekunden einstellbar. Nach Erreichen der Strukturstromdichte ist für eine vorbestimmbare Rampen-Arbeitszeit ein Prozeßstrom mit einer Stromdichte im Bereich von 80% bis 120% der Strukturstromdichte anlegbar. Um eine gleichmäßige Beschichtung zu erreichen, kann die Vorrichtung mit einem Rotationsantrieb zum kontinuierlichen Drehen des Objekts ausgestattet sein. Der Abstand zwischen der Anode und dem zu beschichtenden Objekt wird im Bereich von 1 bis 40 cm, vorzugsweise bei 25 cm gewählt.An anode and a cathode are immersed in the electrolytic bath solution, the object to be coated forming the cathode or being at least part of the cathode. If a chrome electrolyte is used, platinum-plated platinum or PbSn7 are preferably used as the anode material. Anode and cathode are connected to a device for feeding a process current. The process current can be increased from the initial value to the structure current density in several stages, each with a predeterminable change in the current density of 1 to 6 mA / cm 2 per stage. The time intervals between two current increases can be set between 0.1 and 30 seconds. After reaching the structure current density, a process current with a current density in the range of 80% to 120% of the structure current density can be applied for a predeterminable ramp working time. In order to achieve a uniform coating, the device can be equipped with a rotary drive for continuously rotating the object. The distance between the anode and the object to be coated is selected in the range from 1 to 40 cm, preferably at 25 cm.

Die Erfindung ist in den folgenden Ausführungsbeispielen anhand von Zeichnungen näher erläutert. Es zeigen:

Fig. 1
Schematische Darstellung einer Vorrichtung zum galvanischen Aufbringen von Strukturschichten,
Fig. 2
Grafische Darstellung eines zeitlichen Stromdichteverlaufs beim Erzeugen einer Strukturschicht,
Fig. 3
Fotografische Abbildung im Maßstab 200:1 der Oberflächenstruktur eines Objekts, beschichtet nach dem zu Fig. 2 beschriebenen Verfahrensverlauf,
Fig. 4
Fotografische Abbildung im Maßstab 500:1 der in Fig. 3 gezeigten Oberflächenstruktur und
Fig. 5
Grafische Darstellung eines zeitlichen Stromdichteverlaufs beim Erzeugen einer Strukturschicht,
Fig. 6
Grafische Darstellung eines zeitlichen Stromdichteverlaufs beim Erzeugen einer Strukturschicht und
Fig. 7
Grafische Darstellung eines zeitlichen Stromdichteverlaufs beim Erzeugen einer Strukturschicht.
The invention is explained in more detail in the following exemplary embodiments with reference to drawings. Show it:
Fig. 1
Schematic representation of a device for the galvanic application of structural layers,
Fig. 2
Graphical representation of a current density profile over time when generating a structure layer,
Fig. 3
Photographic image on a scale of 200: 1 of the surface structure of an object, coated according to the course of the method described for FIG.
Fig. 4
500: 1 scale photographic image of the surface structure and
Fig. 5
Graphical representation of a current density profile over time when generating a structure layer,
Fig. 6
Graphic representation of a temporal current density curve when generating a structure layer and
Fig. 7
Graphic representation of a temporal current density curve when generating a structure layer.

Fig. 1 zeigt die schematische Darstellung einer Vorrichtung zum galvanischen Aufbringen von Strukturschichten. Ein mit elektrolytischer Flüssigkeit 1 gefüllter Behälter bildet das galvanische Bad. In das galvanische Bad ist ein zu beschichtendes Objekt 2 und eine Anode 3 eingetaucht. Das zu beschichtende Objekt bildet die Kathode 2. Anode und Kathode sind mit einer gesteuerten elektrischen Energiequelle 4 verbunden. Bei der Energiequelle kann es sich um eine Strom- oder um eine Spannungsquelle handeln. Da, was die elektrischen Einflüsse betrifft, der Strom, bzw. die Stromdichte an der Kathode für die Beschichtung maßgebend ist, läßt sich der Prozeß mit einer Stromquelle genauer kontrollieren. Der Einsatz einer Spannungsquelle hat demgegenüber den Vorteil eines geringeren elektrischen Schaltungsaufwands. Solange sich andere Parameter, wie z. B. die Badtemperatur und die Konzentration des Elektrolyts nicht maßgeblich ändern, läßt sich der Prozeß auch mit einer Spannungsquelle gut kontrollieren.Fig. 1 shows the schematic representation of a device for the galvanic application of structural layers. A with electrolytic liquid 1 filled container that galvanic bath. In the galvanic bath is a too coating object 2 and an anode 3 immersed. That too Coating object forms the cathode 2. Anode and cathode are with a controlled electrical energy source 4th connected. The energy source can be an electricity or be a voltage source. There what the affects electrical influences, the current, respectively the Current density at the cathode is decisive for the coating is the process can be more accurate with a power source check. The use of a voltage source has in contrast, the advantage of a lower electrical Circuit effort. As long as other parameters, such as. B. the bath temperature and the concentration of the electrolyte are not The process can also be significantly changed with a Check the voltage source well.

Die elektrische Energiequelle 4 wird von einer programmierbaren Steuereinheit 5 angesteuert. Mit der Steuereinheit lassen sich beliebige zeitliche Spannungs-, bzw. Stromverläufe vorgeben, die dann automatisch über Energiequelle 4 an die Elektroden gelegt werden.The electrical energy source 4 is from a programmable control unit 5 controlled. With the Control unit can be any time voltage, or specify current curves, which are then automatically via Energy source 4 are placed on the electrodes.

Fig. 2 zeigt die grafische Darstellung des zeitlichen Verlaufs der Prozeßstromdichte beim Erzeugen einer Strukturschicht. Die horizontale Achse von Fig. 2 ist die Zeitachse, auf der vertikalen Achse y ist die Stromdichte dargestellt. Dabei handelt es sich um ein Ausführungsbeispiel für einen möglichen Verfahrensablauf, das im Folgenden genauer beschrieben ist. Die Figuren 3 und 4 zeigen fotografische Darstellungen der mit diesem Verfahren erzeugten Strukturschicht.Fig. 2 shows the graphical representation of the temporal Process current density curve when generating a Structural layer. 2 is the horizontal axis Time axis, on the vertical axis y is the current density shown. This is an exemplary embodiment for a possible procedure that follows is described in more detail. Figures 3 and 4 show photographic representations of using this process generated structure layer.

Als galvanisches Bad wird ein schwefelsaurer Chromelektrolyt mit 200 Gramm Chromsäure CrO3 und 2 Gramm Schwefelsäure H2SO4 verwendet. Bei dem zu beschichtenden Werkstück handelt es sich um ein rotationssymmetrisches Bauteil, einen Feuchtreibzylinder für die Druckindustrie. Um eine für die Strukturverchromung geeignete Ausgangsfläche zu schaffen, wird der aus St52 bestehende Zylinder zunächst feingeschliffen, mit einer Rauhtiefe von Rz < 3 µm. Anschließend wird nach in der Galvanotechnik üblichen Bedingungen eine 30 µm dicke Nickelschicht und darauf eine 10 µm dicke, rißarme Chromschicht aufgetragen. Das so vorbereitete Werkstück wird zur Strukturverchromung im galvanischen Bad rotiert, um eine möglichst gleichmäßige Beschichtung zu erreichen. Das Werkstück bildet die Kathode, als Anode wird platiniertes Titan oder PbSn7 verwendet. Der Elektrodenabstand Anode/Kathode wird auf 25 cm eingestellt. A sulfuric acid chromium electrolyte with 200 grams of chromic acid CrO 3 and 2 grams of sulfuric acid H 2 SO 4 is used as the galvanic bath. The workpiece to be coated is a rotationally symmetrical component, a dampening cylinder for the printing industry. In order to create a starting surface suitable for structural chrome plating, the cylinder consisting of St52 is first finely ground, with a roughness depth of Rz <3 µm. A 30 µm thick nickel layer and then a 10 µm thick, crack-free chrome layer are then applied according to the conditions customary in electroplating. The workpiece prepared in this way is rotated for structural chrome plating in the galvanic bath in order to achieve a coating that is as uniform as possible. The workpiece forms the cathode, platinum-plated titanium or PbSn7 is used as the anode. The anode / cathode electrode spacing is set to 25 cm.

Während einer ersten Prozeßphase 7 bleibt der Prozeßstrom abgeschaltet. Diese Phase dient dem Akklimatisieren des Werkstücks an das galvanische Bad. Dabei nimmt das Werkstück die Temperatur des Elektrolyten an. Nach etwa einer Minute wird ein Gleichstrom zwischen Anode und Kathode eingeschaltet. Dieser bleibt während der Phase 8 die etwa 600 Sekunden lang dauert, eingeschaltet. Dabei wird eine Chrom-GLeichstromgrundschicht auf das Werkstück aufgetragen. Die verwendete Stromdichte ist auch beim Normalverchromen üblich, hier 20 mA/cm2. Nach dem Auftrag der Gleichstrom-Grundschicht folgt eine zweite Phase 9 ohne Strom.The process stream remains switched off during a first process phase 7. This phase serves to acclimatize the workpiece to the galvanic bath. The workpiece takes on the temperature of the electrolyte. After about a minute, a direct current between the anode and cathode is switched on. This remains switched on during phase 8, which lasts about 600 seconds. A chrome-G DC base layer is applied to the workpiece. The current density used is also common for normal chrome plating, here 20 mA / cm 2 . After the application of the direct current base layer, a second phase 9 follows without current.

Danach beginnt das eigentliche Erzeugen der Struktur. Während der Phasen 10 und 11 wird die Stromdichte in Stufen auf die Strukturstromdichte 14 erhöht. Die Kenndaten der Stufen (Höhe der Stromstufen und Zeitabstand zwischen zwei Stromschritten) werden dabei während dem Anstieg variiert. In der ersten Phase 10 wird der Strom in 16 Stufen auf 40 mA/cm2 erhöht. Das entspricht einer Änderung der Stromdichte von 2,5 mA/cm2 pro Stufe. Die Zeit 28 zwischen zwei Stromstufen beträgt 5 Sekunden. Danach wird die Stromdichte während der Phase 11 in 62 weiteren Schritten auf die Strukturstromdichte von 100 mA/cm2 erhöht, die Zeit zwischen zwei Stromstufen beträgt 6 Sekunden (der im Graph von Fig. 2 dargestellte Stromdichteverlauf ist nicht maßstabgetreu, dasselbe gilt für die in den Fig. 5 und 6 gezeigten Graphen).Then the actual creation of the structure begins. During phases 10 and 11, the current density is increased in steps to the structure current density 14. The characteristic data of the stages (height of the current stages and time interval between two current steps) are varied during the ascent. In the first phase 10, the current is increased in 16 steps to 40 mA / cm 2 . This corresponds to a change in the current density of 2.5 mA / cm 2 per stage. The time 28 between two current stages is 5 seconds. The current density during phase 11 is then increased in 62 further steps to the structure current density of 100 mA / cm 2 , the time between two current stages is 6 seconds (the current density curve shown in the graph in FIG. 2 is not to scale, the same applies to that in FIG 5 and 6 graphs).

Nachdem die Strukturstromdichte erreicht ist, wird diese Stromdichte während der Rampenarbeitszeit 12 gehalten. Der dabei fließende Gleichstrom führt zum Wachstum der in den Phasen 10 und 11 erzeugten Strukturschicht. Die Dauer der Rampenarbeitszeit beträgt 60 Sekunden. Danach wird die Stromdichte wiederum stufenweise, in 22 Schritten, auf den Endwert von 0 mA/cm2 abgesenkt. Die Zeit zwischen zwei Stromschritten beträgt dabei 4 Sekunden. After the structure current density is reached, this current density is maintained during the ramp working time 12. The direct current flowing thereby leads to the growth of the structural layer produced in phases 10 and 11. The ramp work time is 60 seconds. Then the current density is again gradually reduced in 22 steps to the final value of 0 mA / cm 2 . The time between two current steps is 4 seconds.

Aus anwendungstechnischen Gründen wird im Falle des Feuchtreibzylinders anschließend auf die nach dem erfindungsgemäßen Verfahren hergestellte Chrom-Strukturschicht noch eine 4 bis 8 µm dicke mikrorissige Chromschicht aufgetragen. Dies geschieht unter den in der Galvanotechnik üblichen Gleichstrombedingungen und wird hier nicht näher erläutert.For technical reasons, in the case of Wet friction cylinder then on the after Processes produced according to the invention Chromium structure layer still a 4 to 8 µm thick micro-cracked Chrome layer applied. This happens among those in the Electroplating common DC conditions and will be here not explained in more detail.

Die Fig. 3 und 4 zeigen mikroskopische Aufnahmen der Chrom-Strukturschicht, die nach dem zu Figur 2 beschriebenen Verfahren erzeugt wurde. Die Strukturschicht besteht vorwiegend aus etwa kugelförmigen, einzelnen und teilweise auch aneinanderliegenden Körpern. Die gezeigte Strukturschicht weist eine Oberflächenrauheit von Rz=8 µm bei einem Traganteil von 25% auf. Der "Traganteil" ist auch als "Materialanteil" gemäß DIN 4762 definiert.3 and 4 show microscopic images of the Chromium structural layer according to that described in FIG. 2 Process was generated. The structure layer exists predominantly of spherical, individual and partial also bodies lying against each other. The one shown The structural layer has a surface roughness of Rz = 8 µm a share of 25%. The "load share" is also as "Material proportion" defined in accordance with DIN 4762.

Fig. 5 zeigt den zeitlichen Stromdichteverlauf eines weiteren Verfahrensablaufs zur Strukturbeschichtung. Die Prozeßphasen 7, 8 und 9 wurden bereits in den Ausführungen zu Fig. 2 erörtert. In der darauf folgenden Phase 15 wird die Stromdichte in 110 gleichen Schritten auf die Strukturstromdichte von 100 mA/cm2 erhöht. Die Zeit zwischen zwei Stromschritten beträgt 10 Sekunden. Nach der Rampenarbeitszeit 16 von 60 Sekunden wird die Stromdichte, diesmal in 22 gleichen Schritten, bis auf den Endwert von O mA/cm2 abgesenkt. Die Zeit zwischen zwei Stromschritten beträgt 4 Sekunden. Im Anschluß daran wird nach einem kurzen stromfreien Moment, der Prozeßzyklus bestehend aus den Phasen 15, 16 und 17 wiederholt.5 shows the current density profile over time of a further process sequence for the coating of structures. The process phases 7, 8 and 9 have already been discussed in the explanations for FIG. 2. In the subsequent phase 15, the current density is increased in 110 identical steps to the structure current density of 100 mA / cm 2 . The time between two current steps is 10 seconds. After the ramp working time 16 of 60 seconds, the current density is reduced, this time in 22 identical steps, to the final value of O mA / cm 2 . The time between two current steps is 4 seconds. Following this, after a brief current-free moment, the process cycle consisting of phases 15, 16 and 17 is repeated.

Fig. 6 zeigt den zeitlichen Stromdichteverlauf eines weiteren Verfahrensverlaufs. Nach der Wartephase 7 zum Akklimatisieren des Werkstücks an das galvanische Bad folgt ein Gleichstromimpuls 18, der in seiner Art dem Gleichstromimpuls 8 in Fig. 2 entspricht. Im Anschluß daran folgt direkt eine Keimbildungsphase 19, in der die Stromdichte stufenweise auf die Strukturstromdichte 24 erhöht wird. Die Stromdichte wird dann während der Rampenarbeitszeit 20 auf der Strukturstromdichte gehalten und anschließend, während der Phase 21 rampenförmig auf einen Endwert 26 abgesenkt. Nach einer kurzen Wartezeit 22 folgt erneut eine Keimbildungsphase 23 mit stufenweiser Erhöhung der Stromdichte bis auf die neue Strukturstromdichte 25. Dabei ist die Anfangsstromdichte der Keimbildungsphase 23 gleich dem Endwert 26, auf den die Stromdichte am Ende des vorhergehenden Strukturerzeugungszyklus abgesenkt wurde. Die Stromdichte wird dann während der Rampenarbeitszeit 27 auf der Strukturstromdichte 25 gehalten und im Anschluß daran sprungartig auf den neuen Endwert von 0 mA/cm2 abgesenkt.6 shows the temporal current density profile of a further method profile. After the waiting phase 7 for acclimatizing the workpiece to the galvanic bath, there follows a direct current pulse 18, which corresponds in its nature to the direct current pulse 8 in FIG. 2. This is immediately followed by a nucleation phase 19 in which the current density is gradually increased to the structure current density 24. The current density is then kept at the structure current density during the ramp working time 20 and is then ramped down to an end value 26 during the phase 21. After a short waiting time 22 there follows again a nucleation phase 23 with a gradual increase in the current density up to the new structure current density 25. The initial current density of the nucleation phase 23 is equal to the end value 26 to which the current density was reduced at the end of the previous structure generation cycle. The current density is then kept at the structure current density 25 during the ramp working time 27 and subsequently abruptly reduced to the new final value of 0 mA / cm 2 .

Fig. 7 zeigt den zeitlichen Stromdichteverlauf einer weiteren Variante des Verfahrensablaufs. Die Verfahrensabschnitte 7 bis 9 wurden bereits zu Fig. 2 besprochen. Der Prozeßstrom wird dann während Phase 29 stufenweise auf die Strukturstromdichte 30 erhöht. Danach wird während der Rampenarbeitszeit 32 ein Prozeßstrom mit einem Stromdichtewert von 80% der Strukturstromdichte 30 angelegt. Dazwischen liegt eine stromfreie Ruhezeit 31. Nach Ablauf der Rampenarbeitszeit 32 wird der Prozeßstrom während Phase 33 auf einen Endwert abgesenkt. Dieser Endwert dient als Anfangswert für einen zweiten Strukturerzeugungszyklus, beginnend mit dem stufenweisen Stromanstieg in Phase 35. Nach erreichen der neuen Strukturstromdichte 36 wird während der Rampenarbeitszeit 38 ein Prozeßstrom mit einem Stromdichtewert von 120% der Strukturstomdichte 36 angelegt. Dazwischen liegt wiederum eine stromfreie Ruhezeit 37.7 shows the current density profile of another Variant of the procedure. Process sections 7 to 9 have already been discussed for FIG. 2. The process stream will then be phased in during phase 29 Structure current density 30 increased. After that, during the Ramp working time 32 a process stream with one Current density value of 80% of the structure current density 30 is applied. In between there is a current-free rest period 31. After the Ramp working time 32 becomes the process stream during phase 33 lowered to a final value. This final value serves as Initial value for a second structure generation cycle, starting with the gradual increase in electricity in phase 35. After the new structure current density 36 will be reached during the Ramp working time 38 is a process stream with one Current density value of 120% of the structure current density 36 is applied. In between there is again a current-free rest 37.

Claims (12)

  1. Process for the electrochemical (galvanic) application of a surface coating to a machine component, by means of a direct current application process, the formation of nuclei of the deposition material on the area to be coated being achieved by means of at least one starting pulse of the electrical voltage and/or the electrical current, and subsequently a growth of the deposition material nuclei being brought about by means of at least one following pulse, as a result of the addition of further deposition material, characterized in that, during the nucleus formation phase, the increase in the electrical voltage and/or the electrical current is carried out in a plurality of stages, the time between the increases lying between 0.1 and 30 seconds, current density changes being carried out in stages of 1 to 6 mA/cm2.
  2. Process according to Claim 1, characterized in that the stages are increased with in each case a predefinable change of the current density of 1 to 6 mA/cm2 per stage, from a starting value to a structuring current density (14, 24, 25), the increases are increases in current density, and the stages are applied to the bath in a sufficient number until a structure layer, consisting of a deposit of individually superimposed, approximately spherical or dendritic bodies, is achieved on the surface of the object, and thereafter in a nucleus growth phase, during a predeterminable ramp working time (12, 16), a process current having a current density in the range from 80% to 120% of the structuring current density is applied.
  3. Process according to Claim 1 or 2, characterized in that the duration of the individual stages is about 7 seconds.
  4. Process according to at least one of Claims 1 to 3, characterized in that the current density is increased in 10 to 240 stages.
  5. Process according to at least one of Claims 1 to 4, characterized in that the structuring current density (14, 24, 25) lies in the range from 30 mA/cm2 to 180 mA/cm2.
  6. Process according to at least one of Claims 1 to 5, characterized in that the ramp working time (12, 16) is 1 to 600 seconds, preferably about 30 seconds.
  7. Process according to at least one of Claims 1 to 6, characterized in that the process current is reduced to a final value (26) after the ramp working time has elapsed.
  8. Process according to Claim 7, characterized in that the process current, after the ramp working time has elapsed, is lowered to the final value in stages with in each case a predefined change of -1 to -8 mA/cm2 per stage.
  9. Process for the application of'a surface coating to the electrically conductive surface of an object, characterized in that the process according to one of Claims 7 or 8 is repeated cyclically two to twenty times, in each case the final value of the preceding cycle corresponding to the starting value of the following cycle.
  10. Process according to Claim 9, characterized in that the final values (26) have different levels.
  11. Process according to at least one of Claims 1 to 10, characterized in that, before the generation of the structure, a direct current pulse (8, 18) having a current density of 15 to 60 mA/cm2 is applied in order to build up a direct current base layer.
  12. Use of the process according to at least one of Claims 1 to 11, characterized in that it is applied
    in order to generate structure on cylinder surfaces for lubricant stores for the accommodation of lubricants,
    in order to set defined degrees of reflectance of surfaces in optical and medical instruments and for functional and decorative applications in the furniture and sanitary fittings industry,
    in order to generate surfaces with defined roughness in products in the graphics industry,
    in order to generate structured surfaces on tools.
EP94928407A 1993-10-07 1994-10-01 Process for the galvanic application of a surface coating Expired - Lifetime EP0722515B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4334122 1993-10-07
DE4334122A DE4334122C2 (en) 1992-04-09 1993-10-07 Process for electrochemically applying a surface coating and application of the process
PCT/EP1994/003314 WO1995009938A1 (en) 1993-10-07 1994-10-01 Process for the galvanic application of a surface coating

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EP0722515A1 EP0722515A1 (en) 1996-07-24
EP0722515B1 true EP0722515B1 (en) 1998-01-28

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JP (1) JP3293828B2 (en)
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CN (1) CN1044395C (en)
AU (1) AU7784794A (en)
BR (1) BR9405631A (en)
CA (1) CA2172613C (en)
CH (1) CH690273A5 (en)
CZ (1) CZ286909B6 (en)
DE (1) DE59405190D1 (en)
ES (1) ES2114703T3 (en)
FI (1) FI103674B1 (en)
GR (1) GR3026689T3 (en)
PL (1) PL177073B1 (en)
SI (1) SI9420006B (en)
SK (1) SK281999B6 (en)
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1441157A1 (en) 2003-01-21 2004-07-28 Fuchs Technology AG Cylinder surface
EP3000918A1 (en) 2014-09-24 2016-03-30 topocrom systems AG Method and device for the galvanic application of a surface coating
US11136685B2 (en) 2015-11-05 2021-10-05 Topocrom Systems Ag Method and device for the galvanic application of a surface coating
EP4012074A1 (en) 2020-12-14 2022-06-15 topocrom systems AG Surface coating and method for the production thereof

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19828545C1 (en) 1998-06-26 1999-08-12 Cromotec Oberflaechentechnik G Galvanic bath for forming a hard chromium layer on machine parts
US6478943B1 (en) 2000-06-01 2002-11-12 Roll Surface Technologies, Inc. Method of manufacture of electrochemically textured surface having controlled peak characteristics
WO2003004732A1 (en) * 2001-07-05 2003-01-16 Roll Surface Technologies, Inc. Electrochemically textured surface having controlled peak characteristics and the method of manufacture
DE10255853A1 (en) 2002-11-29 2004-06-17 Federal-Mogul Burscheid Gmbh Manufacture of structured hard chrome layers
DE102004019370B3 (en) 2004-04-21 2005-09-01 Federal-Mogul Burscheid Gmbh Production of optionally coated structurized hard chrome layer, used e.g. for decoration, protection or functional coating on printing roller or stamping, embossing or deep drawing tool uses aliphatic sulfonic acid in acid plating bath
DE102008017270B3 (en) 2008-04-04 2009-06-04 Federal-Mogul Burscheid Gmbh Structured chromium solid particle layer and method for its production and coated machine element
AT506076B1 (en) * 2008-06-03 2009-06-15 Vassilios Dipl Ing Polydoros METHOD FOR PRODUCING NANOSTRUCTURED CHROMIUM LAYERS ON A SUBSTRATE
EP2149447A1 (en) 2008-07-29 2010-02-03 Alcan Technology &amp; Management Ltd. Method for producing a sheet of material with surface structure
CN102877098B (en) * 2012-10-29 2015-06-17 东莞市若美电子科技有限公司 Multi-waveband output pulse plating method
CN105734631B (en) * 2014-12-10 2019-03-19 上海宝钢工业技术服务有限公司 The electro-plating method of roll for cold rolling frosting treatment
CN110117802B (en) * 2019-05-06 2020-05-22 浙江大学 Preparation method of multistage three-dimensional microstructure
CN111962120A (en) * 2020-08-18 2020-11-20 重庆佰鸿机械设备有限公司 Pipe fitting inner wall surface treatment process

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD134785A1 (en) * 1978-01-25 1979-03-21 Hans Skilandat METHOD FOR THE ELECTROLYTIC PRODUCTION OF A COPPER SHELF ON COPPER FOIL
US4468293A (en) * 1982-03-05 1984-08-28 Olin Corporation Electrochemical treatment of copper for improving its bond strength
US5185073A (en) * 1988-06-21 1993-02-09 International Business Machines Corporation Method of fabricating nendritic materials
DE4211881C2 (en) * 1992-04-09 1994-07-28 Wmv Ag Process for the electrochemical application of a structured surface coating

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1441157A1 (en) 2003-01-21 2004-07-28 Fuchs Technology AG Cylinder surface
DE10302107A1 (en) * 2003-01-21 2004-07-29 Fuchs Technology Ag cylinder surface
EP3000918A1 (en) 2014-09-24 2016-03-30 topocrom systems AG Method and device for the galvanic application of a surface coating
US11136685B2 (en) 2015-11-05 2021-10-05 Topocrom Systems Ag Method and device for the galvanic application of a surface coating
US11732373B2 (en) 2015-11-05 2023-08-22 Topocrom Systems Ag Method and device for the galvanic application of a surface coating
EP4012074A1 (en) 2020-12-14 2022-06-15 topocrom systems AG Surface coating and method for the production thereof

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WO1995009938A1 (en) 1995-04-13
SK281999B6 (en) 2001-10-08
CA2172613C (en) 2003-06-17
CN1044395C (en) 1999-07-28
SK86195A3 (en) 1996-03-06
ES2114703T3 (en) 1998-06-01
FI952774A (en) 1995-06-06
CZ286909B6 (en) 2000-08-16
CA2172613A1 (en) 1995-04-13
CZ144795A3 (en) 1996-07-17
JPH09503550A (en) 1997-04-08
JP3293828B2 (en) 2002-06-17
DE59405190D1 (en) 1998-03-05
AU7784794A (en) 1995-05-01
GR3026689T3 (en) 1998-07-31
BR9405631A (en) 1999-09-08
CN1115583A (en) 1996-01-24
FI952774A0 (en) 1995-06-06
PL177073B1 (en) 1999-09-30
SI9420006B (en) 2002-02-28
FI103674B (en) 1999-08-13
FI103674B1 (en) 1999-08-13
CH690273A5 (en) 2000-06-30
SI9420006A (en) 1995-12-31
PL309286A1 (en) 1995-10-02
EP0722515A1 (en) 1996-07-24
KR100332077B1 (en) 2002-10-31

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