EP0565070A1 - Electroplating process - Google Patents

Electroplating process Download PDF

Info

Publication number
EP0565070A1
EP0565070A1 EP93105726A EP93105726A EP0565070A1 EP 0565070 A1 EP0565070 A1 EP 0565070A1 EP 93105726 A EP93105726 A EP 93105726A EP 93105726 A EP93105726 A EP 93105726A EP 0565070 A1 EP0565070 A1 EP 0565070A1
Authority
EP
European Patent Office
Prior art keywords
characterized
method according
preceding
pulse
μm
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.)
Granted
Application number
EP93105726A
Other languages
German (de)
French (fr)
Other versions
EP0565070B1 (en
Inventor
Karl Müll
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.)
Winterthurer Metallveredelung AG
Heidelberger Druckmaschinen AG
Original Assignee
Winterthurer Metallveredelung AG
Heidelberger Druckmaschinen AG
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
Priority to DE4211881 priority Critical
Priority to DE4211881A priority patent/DE4211881C2/en
Application filed by Winterthurer Metallveredelung AG, Heidelberger Druckmaschinen AG filed Critical Winterthurer Metallveredelung AG
Publication of EP0565070A1 publication Critical patent/EP0565070A1/en
Application granted granted Critical
Publication of EP0565070B1 publication Critical patent/EP0565070B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/16Electroplating with layers of varying thickness, e.g. rough surfaces; Hull cells
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10Electroplating with more than one layer of the same or of different metals
    • C25D5/12Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • C25D5/14Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/18Electroplating using modulated, pulsed or reversing current

Abstract

The invention relates to a process for electrochemical (electro-)deposition of a surface coating on an object, in particular a roller of a machine, employing an electrical variable, which effects the application of the coating, of the electroplating process. It is provided that, in order to achieve a desired, structured surface topography by means of at least one initial pulse of the electrical variable, nuclei of the deposition material are formed on the face to be coated, and that then, by means of at least one subsequent pulse, growth of the deposition material nuclei is brought about by accretion of further deposition material. <IMAGE>

Description

  • The invention relates to a method for the electrochemical (galvanic) application of a surface coating to an object, preferably a machine component, in particular a machine roller, using an electrical variable of the galvanic process which causes the layer application.
  • In many areas of technology, for example, machine components with special surface properties are required. It is known to apply surface coatings to machine components by means of galvanic processes. If one considers, for example, machine rollers or cylinders for the graphic industry, for example for textile printing or cylinders for printing machines, these are required, among other things, with regard to dampening cylinders with a special, "rough" surface. To produce such surface qualities, the dampening cylinder is hard chrome-plated and then subjected to a customized grinding process. This is followed by a structure etching in order to bring about the desired roughness of the surface.
  • A hard chrome layer is then applied to the surface structure created in this way. These various work steps required for the creation are quite complex and require complicated process engineering. The costs are essentially determined by the complex processing steps such as mechanical grinding to size and chemical structure etching; these machining processes are relatively expensive.
  • The invention is therefore based on the object of specifying a method for the electrochemical application of a surface coating to an object, which enables the desired, structured surface topographies to be created in a simple and inexpensive manner.
  • This object is achieved in that, in order to achieve the desired structured surface topography, nucleation of the deposition material takes place on the surface to be coated by means of at least one initial impulse of the electrical quantity and that the deposition material nuclei are subsequently grown by the addition of further deposition material by means of at least one subsequent impulse. This procedure according to the invention leads to a uniform, optimal structuring of the surface without the need for complex intermediate grinding as well as chemical etching processes. Rather, the desired surface structure is set during the galvanic coating process. It is essential here that the nucleation with separating material is first carried out by means of the initial impulse of the electrical quantity and that the germs formed are subsequently grown by the subsequent impulse.
  • According to a development of the invention, it is provided that an electrical voltage and / or an electrical current is used as the electrical variable such that the initial pulse and / or the subsequent pulse have a defined shape by means of a corresponding voltage and / or current function as a function of time Has.
  • On the basis of the procedure according to the invention, it is possible to produce the structured surface coatings, preferably by means of galvanic chrome or chromium alloy electrolytes, by means of galvanic nickel or nickel alloy electrolytes, by means of galvanic cobalt or cobalt alloy electrolytes, by means of galvanic copper or copper alloy electrolytes or by means of galvanic noble metal or noble metal alloy electrolytes. With the structure of the surface created according to the invention, the requirements of the most varied fields of application can be met. For example, the structure forms defined lubricant deposits or has a storage capacity for substances that come into contact with the surface. In addition, the structuring leads to low-glare devices, for example in medical or optical technology. In this way, precisely defined degrees of reflection can be achieved, such as for functional but also needed for decorative applications. In particular, it is possible with the method according to the invention to coat rollers for printing machines, in particular dampening cylinders from dampening units of such printing machines, which have optimal properties for the printing process.
  • According to a preferred embodiment of the invention, a multilayer structure is provided, at least one of the layers being provided with the structured surface topography. In the course of this multilayer structure, a nickel strike layer is preferably first applied to the object. This nickel strike layer is applied with a thickness of 0.2 to 2 μm, preferably <1 μm. As with all the layers mentioned below, the application is preferably carried out by means of a galvanic process. The object is, for example, a roller or a cylinder of a printing press. The cylinder is preferably made of steel (St.52 / Nirosta).
  • A sulfamate-nickel layer is applied to the nickel strike layer. This layer is preferably produced with a thickness of 25 to 40 μm, in particular 30 μm.
  • It is particularly advantageous if a chromium layer, in particular a low-crack chromium layer, is applied to the sulfamate-nickel layer. This chrome layer preferably has a thickness of 5 up to 15 µm, in particular from 10 µm. The structured surface coating generated by means of the initial and subsequent pulse is now applied to the chrome layer. This surface coating is preferably designed as a structured chromium layer, a chromium or a chromium alloy electrolyte being used in the galvanic process. According to the invention, the application is carried out by first applying germs of the deposition material to the surface to be coated (for example the mentioned chrome layer) by means of at least one initial pulse of the electrical quantity of the galvanic process. Subsequently, growth of these germs is then brought about by means of at least one subsequent pulse until the desired structuring is achieved. The structured surface coating is preferably produced with a maximum thickness of 5 to 20 μm, preferably 7 to 10 μm. The "maximum thickness" is understood to mean the measure up to the highest elevations, because due to the structuring, that is to say higher and lower lying areas, a thickness measure specification is not otherwise clearly defined. The so-called "load share", which is also defined as the "material share" according to DIN 4762, can also be used as the design. This load share is the percentage ratio of the length of the profile cut in a certain cutting line to a reference distance. The profile results from the surface structure, the cutting line being below the highest elevations of the structure, so that it cuts the corresponding elevations leads in some areas between the surveys. The method according to the invention preferably achieves a load share of 25%, the cutting line being 2 μm below the highest point of the structure.
  • According to a preferred embodiment of the invention it is provided that a finishing layer of micro-cracked chromium is applied to the structured surface coating. This final layer is preferably produced with a thickness of 5 to 20 μm, in particular 8 to 10 μm.
  • While the structured surface coating produced by the method according to the invention has the correspondingly desired roughness or the correspondingly desired load-bearing component, the other layers mentioned here (nickel strike layer, sulfamate-nickel layer, low-crack chrome layer (base layer) and finishing layer made of micro-cracked chromium ) on the other hand, to be regarded as having the same thickness and unstructured.
  • According to a preferred embodiment of the invention, it is provided that a chromium electrolyte is used for the electrochemical process for applying the structured surface coating. This chrome electrolyte preferably has a temperature of about 45 ° C.
  • It is advantageous if the object is set in rotation while the structured surface coating is being applied. Preferably this takes place in the cylinders of the printing presses mentioned in that they are rotated about their longitudinal central axis.
  • Anodes made of PbSn7 or platinized titanium are particularly preferably used when applying the structured surface coating. In contrast, the object to be coated forms the cathode when the structured surface coating is applied.
  • It has proven to be particularly advantageous if, when the structured surface coating is applied, there is an electrode distance between the anode and cathode of 10 to 40 cm, in particular 25 cm.
  • A trapezoidal initial voltage pulse and also an approximately trapezoidal subsequent voltage pulse are preferably used to generate the structure of the surface coating. First, in the course of the process, the machine component is immersed in the electrolytes, in particular chrome electrolytes, and the initial impulse is only started after a voltage-free or current-free waiting time. This waiting time serves, among other things, to adjust the temperature, i.e. the base material (machine component) assumes approximately the temperature of the electrolyte. This waiting time is preferably 60 s.
  • Furthermore, it is advantageous if between the end of the initial pulse and the beginning of the subsequent pulse a voltage or current-free intermediate period elapses. This intermediate period is thus between the period of the nucleation mentioned above and the growth phase of the deposition process.
  • According to a preferred embodiment, in order to form the structured surface coating, it is provided that a basic pulse (voltage or current pulse) is connected upstream of the initial pulse. This serves to build up a base layer already mentioned above. The basic pulse preferably has an initial edge with a slope of δU / δt = approx.0.25 V / 5 s
    Figure imgb0001
    . This initial edge is maintained until there is an amplitude of approximately 4 V. This is maintained with a constant value over a period of approximately 600 s. The basic pulse ends with a drop of δU / δt = approx.0.4 V / 5 s
    Figure imgb0002
    , with this drop following the constant amplitude and ending in the voltage or current-free state. This completes the basic pulse and a voltage or current-free resting phase now occurs, which follows the end flank of the basic pulse and ends with the initial pulse for inducing nucleation.
  • This initial pulse receives a starting edge that has a slope of δU / δt = approx. 0.3 V / 5 s
    Figure imgb0003
    has, this slope is maintained up to an amplitude of about 5 V. When this amplitude is reached, the initial pulse is complete. A starting edge of a follows the initial pulse Follow pulse on, the starting edge of the follow pulse an increase of δU / δt = approx.0.1 V / 6 s
    Figure imgb0004
    having. This starting edge increases the current in the galvanic process up to a maximum current of approx. 950 A based on a standard area. This maximum current is now maintained over a period of approximately 60s. The following pulse is then shut down, that is to say it has a trailing edge, which has a drop of δU / δt = approx.0.5 V / 4 s
    Figure imgb0005
    provided and shut down until there is no current or voltage. This creates the desired, structured surface topography on the object (machine component).
  • To vary the surface topography, it is possible to vary the aforementioned voltage and / or current values and / or voltage difference values and / or time and / or time difference values. This variation is possible, based on the exemplary embodiment mentioned, with deviations of ± 10%, preferably ± 5%.
  • The drawings illustrate the invention, in which:
  • Figure 1
    2 shows a longitudinal section through a dampening cylinder of a dampening unit of a printing press,
    Figure 2
    2 shows an enlarged sectional view through a surface layer structure of the dampening friction cylinder of FIG. 1,
    Figure 3
    a voltage-time diagram of a galvanic coating process for applying a structured surface coating,
    Figure 4
    a representation of the structured surface coating in 200x magnification,
    Figure 5
    the structured surface coating of Figure 4, but with 500x magnification,
    Figure 6
    a surface coating produced according to the prior art and
    Figure 7
    a surface coating produced by the method according to the invention.
  • FIG. 1 shows a longitudinal section through a dampening cylinder 1 of a printing press. The dampening cylinder 1 has a cylindrical base body 2, the outer surface 3 of which is provided with a layer structure 4. The layer structure 4 is identified by the dash-dot line in FIG. 1. It is guided around the edge regions 5 of the dampening cylinder 1 with the length of a portion of the radius.
  • The layer structure 4 is composed of individual layers, each of which is applied electrochemically, that is to say by means of galvanic processes.
  • FIG. 2 shows a section through the layer structure 4. A nickel strike layer 6 is electrodeposited on the base body 2 of the dampening cylinder 1. The basic body is made of steel St.52 / Nirosta. The nickel strike layer 6 is a pre-nickel plating. The electrolyte used for this is very acidic with a high chloride concentration. The nickel strike layer 6 has a uniform thickness of preferably 1 to 2 μm.
  • A sulfamate-nickel layer 7 is applied electrolytically to the nickel strike layer 6. This sulfamate-nickel layer 7 is sulfur-free; it has a thickness of 30 to 40 µm and a Vickers hardness of 200 to 250 HV.
  • A low-crack chrome layer 8 is electroplated onto the sulfamate-nickel layer 7; it has a uniform thickness of 10 to 15 µm and forms a so-called base layer.
  • A structured surface coating 9 is applied to the chrome layer 8 by means of a galvanic process. This surface coating 9 represents a structured chrome layer 10. Due to the structuring, there are corresponding elevations and depressions, the maximum thickness, measured from the sole to the apex of the maximum elevation, of this structured chrome layer 10 being 7 to 10 μm.
  • A uniformly thick final layer 11, which consists of micro-cracked chromium, is applied galvanically to the structured surface coating 10. Its thickness is preferably 8 to 10 microns. The hardness is about 900 HV or greater than 900 HV.
  • Overall, a surface of the dampening cylinder 1 with a roughness Rz = 6 to 10 μm is thus provided.
  • FIG. 3 shows a voltage-time diagram which illustrates the control of an electrical variable (voltage U) of the galvanic process for applying the base layer and for subsequently applying the structured surface coating 9. For the electrochemical process, the dampening cylinder 1 is switched as a cathode and anodes made of PbSn7 or platinized titanium are used. The electrode distance between the anode and cathode is set to approx. 25 cm. The dampening cylinder 1 is continuously rotated about its longitudinal axis 12 (FIG. 1) while the structured surface coating 9 is being applied.
  • According to FIG. 3, the electrochemical process for applying the base layer (chrome layer 8) and the structured surface coating 9 is carried out as follows:
  • First, the base body 2 of the dampening cylinder 1 is introduced into a chrome electrolyte with a temperature of approx. 45 ° C., after which Initially, a waiting time t w passes, which is approximately 60 s long. During this time (without applying current or voltage), the temperature of the base material (base body 2) is adjusted to the electrolyte temperature.
  • For the application of the base layer (chrome layer 8), an electrical base pulse 13 is first applied between the anode and cathode after the waiting time t w . Then, by means of an initial and a subsequent pulse 14, nucleation of the separating material (initial pulse 14 ') and then growth of the separating material nuclei by addition with further separating material is then brought about (subsequent pulse 14''), as a result of which the structured surface coating 9 is formed.
  • The basic pulse 13 and the initial and subsequent pulse 14 are designed as follows: The basic pulse 13 is a voltage pulse with a trapezoidal shape. The start and follow pulse 14 is also a voltage pulse, which is composed of the start pulse 14 'and the directly following pulse 14''and also has a trapezoidal shape; the pure trapezoidal shape is disturbed insofar as the starting edge (leading edge) of the initial pulse 14 'has a different slope than the starting edge of the subsequent pulse 14''. This will be discussed in more detail below.
  • The basic pulse 13 has an initial edge 15 which starts after the waiting time t w and an increase of δU / δt = 0.25 V / 5 s
    Figure imgb0006
    having. A constant amplitude 16 with 4 V over a period of 600 s connects to the starting edge 15. This is followed by an end flank 17, which has a drop of δU / δt = 0.4 V / 5 s
    Figure imgb0007
    having. An intermediate time period t z then follows, which is current-free or voltage-free and has a length of 60 s. The starting pulse 14 'then follows with a starting edge 18, this having an increase of δU / δt = 0.3 V / 5 s
    Figure imgb0008
    having. This slope is carried out up to an amplitude A of 5 V. The initial pulse 14 'ends here. This is indicated by the dashed line 22. The starting edge 20 of the following pulse 14 ″ immediately follows the starting pulse 14 ′, which has an incline δU / δt = 0.1 V / 6 s
    Figure imgb0009
    having. By means of this starting edge 20, the current on which the galvanic process is based is increased to a maximum current I max of 950 A. This maximum current I max is maintained over a period of 60 s. This is followed by a trailing edge 21 of the subsequent pulse 14 ″, which drops from δU / δt = 0.5 V / 4 s
    Figure imgb0010
    having. At the end of the trailing edge 21 there is no current or voltage.
  • In FIG. 3, the total flank formed by the initial pulse 14 'and the subsequent pulse 14''is designated by 19. It is composed of the two starting edges 18 and 20.
  • By means of the described electrochemical process for applying the structured surface coating 9, a roughness Rz = 9 μm is achieved with a load share of 25%.
  • Subsequently, the finishing layer 11 is applied to the structured surface coating 9 produced according to the invention using a conventional electrochemical process.
  • FIG. 4 shows the structure chrome of the structured surface coating 9 in a 200-fold magnification. FIG. 5 shows a 500-fold magnification. It can be clearly seen that there is a very uniform structured distribution. FIGS. 6 and 7 show a comparison of a known surface coating with the surface coating according to the invention: namely, FIG. 6 shows a conventional surface coating subjected to a grinding and etching process in 200 times magnification and FIG. 7 shows the structured surface coating 9 according to the invention, also in FIG 200x magnification. It can be clearly seen that the structure according to the invention is constructed in a substantially more uniform and orderly manner than in the case of the prior art.
  • When a dampening cylinder 1 is created, a degreasing process and a de-papering are of course carried out first, as is customary, before the layer structure 4 is applied. These processes may also be repeated several times.
  • Only then is the nickel strike layer 6, then the sulfamate nickel layer 7 and then the chrome layer 8 applied. The structured surface coating 9 is then deposited and then the final layer 10 is applied, which consists of micro-cracked chromium and with which the dimensional accuracy can be controlled.
  • As already mentioned at the beginning, the invention is not limited to chromium or chromium alloy layers, but can also be carried out with other deposition materials.
  • Furthermore, according to a further exemplary embodiment, not shown, it is possible to insert a current-free or voltage-free pause, namely an intermediate period, between the initial pulse and the subsequent pulse.

Claims (33)

  1. Process for the electrochemical (galvanic) application of a surface coating to an object, preferably a machine component, in particular a machine roller, using an electrical quantity of the galvanic process which effects the layer application, characterized in that in order to achieve a desired structured surface topography by means of at least one initial pulse (14 ') of the electrical size on the surface to be coated nucleation of the separating material take place and that subsequently the growth of the separating material nuclei is brought about by the addition of further separating material by means of at least one subsequent pulse (14'').
  2. Method according to Claim 1, characterized in that an electrical voltage (U) and / or an electrical current is used as the electrical variable such that the initial pulse (14 ') and / or the subsequent pulse (14'') has a defined shape by a corresponding one Has voltage and / or current function depending on the time (t).
  3. Method according to one of the preceding claims, characterized in that a nickel strike layer (6) is applied to the object.
  4. Method according to one of the preceding claims, characterized in that the nickel strike layer (6) has a thickness of 0.2 µm to 2 µm, preferably <1 µm.
  5. Method according to one of the preceding claims, characterized in that a sulfamate-nickel layer (7) is applied to the nickel strike layer (6).
  6. Method according to one of the preceding claims, characterized in that the sulfamate-nickel layer (7) is produced with a thickness of 25 µm to 40 µm, in particular of 30 µm.
  7. Method according to one of the preceding claims, characterized in that a chromium layer (8), in particular a low-crack chromium layer, is applied to the sulfamate-nickel layer (7).
  8. Method according to one of the preceding claims, characterized in that the chrome layer (8) is produced with a thickness of 5 µm to 15 µm, in particular of 10 µm.
  9. Method according to one of the preceding claims, characterized in that the chrome layer (8) is a base layer which is applied galvanically by means of an electrical base pulse (13).
  10. Method according to one of the preceding claims, characterized in that on the chrome layer (8) the structured surface coating (9) produced by means of the initial and subsequent pulse (14, or 14 'and 14'') is applied.
  11. Method according to one of the preceding claims, characterized in that the structured surface coating (9) is designed as a structured chrome layer (10).
  12. Method according to one of the preceding claims, characterized in that the structured surface coating (9) is produced with a maximum thickness of 5 µm to 20 µm, preferably 7 µm to 10 µm.
  13. Method according to one of the preceding claims, characterized in that a finishing layer (11) made of micro-cracked chromium is applied to the structured surface coating (9).
  14. Method according to one of the preceding claims, characterized in that the closing layer (11) is produced with a thickness of 5 µm to 20 µm, in particular 8 µm to 10 µm.
  15. Method according to one of the preceding claims, characterized in that a chromium electrolyte is used for the electrochemical process for applying the structured surface coating (9).
  16. Method according to one of the preceding claims, characterized in that the chromium electrolyte has a temperature of approximately 45 ° C.
  17. Method according to one of the preceding claims, characterized in that the object is set in rotation during the application of the structured surface coating (9).
  18. Method according to one of the preceding claims, characterized in that anodes made of PbSn7 or platinized titanium are used when applying the structured surface coating (9).
  19. Method according to one of the preceding claims, characterized in that the object, in particular the machine component to be coated, forms the cathode when the structured surface coating (9) is applied.
  20. Method according to one of the preceding claims, characterized in that when the structured surface coating (9) is applied, an electrode distance between the anode and cathode of 10 cm to 40 cm, in particular 25 cm, is maintained.
  21. Method according to one of the preceding claims, characterized in that an approximately trapezoidal voltage pulse is used to generate the structure of the surface coating (9).
  22. Method according to one of the preceding claims, characterized in that to form the the chrome layer (8) forming the base layer, the object, in particular the machine component, is immersed in the electrolyte, in particular chrome electrolyte, and the initial pulse (14 ') is only started after a voltage-free or current-free waiting time (t w ).
  23. Method according to one of the preceding claims, characterized in that a voltage-free or current-free intermediate time period (t z ) elapses between the end of the basic pulse (13) and the beginning of the initial pulse (14 ').
  24. Method according to one of the preceding claims, characterized in that the basic pulse (13) has an initial flank (15) with a slope of δU / δt = approx.0.25 V / 5 s
    Figure imgb0011
    receives.
  25. Method according to one of the preceding claims, characterized in that the initial flank (15) is followed by a constant amplitude of approximately 4 V over a period of approximately 600 s.
  26. Method according to one of the preceding claims, characterized in that the basic pulse (13) has an end flank (17) following the constant amplitude with a drop of δU / δt = approx.0.4 V / 5 s
    Figure imgb0012
    receives.
  27. Method according to one of the preceding claims, characterized in that the intermediate period (t z ) adjoins the end flank (17).
  28. Method according to one of the preceding claims, characterized in that the initial pulse (14 ') has a starting flank (18) with a gradient of δU / δt = approx. 0.3 V / 5 s
    Figure imgb0013
    receives, this slope is maintained up to an amplitude (A) of about 5 V.
  29. Method according to one of the preceding claims, characterized in that the start pulse (14 ') is followed by the follow-up pulse (14'') immediately (without a pause) and that the end of the start edge (18) of the start pulse (14') is continuous (without jumps) ) passes into the beginning of the start edge (20) of the following pulse (14 '').
  30. Method according to one of the preceding claims, characterized in that the starting flank (20) of the following pulse (14 '') has an incline of δU / δt = approx.0.1 V / 6 s
    Figure imgb0014
    The current is increased up to a maximum current (I max ) of approx. 950 A based on a standard area.
  31. Method according to one of the preceding claims, characterized in that the maximum current strength (I max ) is maintained over a period of approximately 60 s.
  32. Method according to one of the preceding claims, characterized in that the subsequent pulse (14 '') has a back flank (21) which adjoins the maximum current (I max ) and which has a drop of δU / δt = approx.0.5 V / 4 s
    Figure imgb0015
    Mistake and is shut down until there is no current or voltage.
  33. Method according to one of the preceding claims, characterized in that the aforementioned voltage and / or current values and / or voltage difference values and / or time and / or time difference values with deviations of ± 10%, preferably ± 5%, are used.
EP93105726A 1992-04-09 1993-04-07 Electroplating process Expired - Lifetime EP0565070B1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE4211881 1992-04-09
DE4211881A DE4211881C2 (en) 1992-04-09 1992-04-09 Process for the electrochemical application of a structured surface coating

Publications (2)

Publication Number Publication Date
EP0565070A1 true EP0565070A1 (en) 1993-10-13
EP0565070B1 EP0565070B1 (en) 1997-07-30

Family

ID=6456427

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93105726A Expired - Lifetime EP0565070B1 (en) 1992-04-09 1993-04-07 Electroplating process

Country Status (4)

Country Link
US (1) US5415761A (en)
EP (1) EP0565070B1 (en)
AT (1) AT156201T (en)
DE (1) DE4211881C2 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3438330A1 (en) 2017-08-03 2019-02-06 Groz-Beckert KG Textile machine component and method for producing a textile tool

Families Citing this family (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SI9420006B (en) * 1993-10-07 2002-02-28 Romabau-Holding Ag Process for the galvanic application of a surface coating
US5958207A (en) * 1994-10-01 1999-09-28 Heidelberger Druckmaschinen Ag Process for applying a surface coating
DE4432512C2 (en) * 1994-09-13 1998-12-17 Lpw Chemie Gmbh Use of a process for the electrolytic deposition of chrome layers
US5958604A (en) * 1996-03-20 1999-09-28 Metal Technology, Inc. Electrolytic process for cleaning and coating electrically conducting surfaces and product thereof
US7556722B2 (en) 1996-11-22 2009-07-07 Metzger Hubert F Electroplating apparatus
US8298395B2 (en) 1999-06-30 2012-10-30 Chema Technology, Inc. Electroplating apparatus
DE19828545C1 (en) 1998-06-26 1999-08-12 Cromotec Oberflaechentechnik G Galvanic bath for forming a hard chromium layer on machine parts
AU1298299A (en) * 1998-11-03 2000-05-22 Johns Hopkins University, The Copper metallization structure and method of construction
US6309969B1 (en) 1998-11-03 2001-10-30 The John Hopkins University Copper metallization structure and method of construction
DE19902527B4 (en) * 1999-01-22 2009-06-04 Hydro Aluminium Deutschland Gmbh Printing plate support and method for producing a printing plate support or an offset printing plate
DE19914136B4 (en) * 1999-03-27 2009-02-26 Koenig & Bauer Aktiengesellschaft Surface for machine parts in printing machines
US6478943B1 (en) 2000-06-01 2002-11-12 Roll Surface Technologies, Inc. Method of manufacture of electrochemically textured surface having controlled peak characteristics
US6670308B2 (en) * 2002-03-19 2003-12-30 Ut-Battelle, Llc Method of depositing epitaxial layers on a substrate
DE10214618B4 (en) * 2002-04-03 2007-07-12 Robert Bosch Gmbh Method for processing workpieces by means of a machining method, in particular the electrochemical machining method
DE10214989A1 (en) * 2002-04-04 2003-10-30 Georg Frommeyer Pressure cylinder used in a printing machine comprises a surface coating made from either a pure nickel layer, a mixed crystal alloy, composite layers or multiple layer systems for engraving a stepped ensemble
AT412556B (en) * 2002-10-04 2005-04-25 Miba Gleitlager Gmbh Method for manufacturing at least one lageraugewichen workpiece
DE10344722B4 (en) * 2002-10-04 2007-11-29 Miba Gleitlager Gmbh Method for producing a workpiece having at least one bearing eye
DE10251614A1 (en) * 2002-11-06 2004-05-19 Paul Kronenberger Production of a uniform defined surface structure on an electrically conducting workpiece comprises depositing a layer matrix made from a metal or metal alloy with embedded particles on the workpiece surface
DE10255853A1 (en) 2002-11-29 2004-06-17 Federal-Mogul Burscheid Gmbh Manufacture of structured hard chrome layers
DE10302107A1 (en) * 2003-01-21 2004-07-29 Fuchs Technology Ag cylinder surface
DE10361888B3 (en) * 2003-12-23 2005-09-22 Airbus Deutschland Gmbh Anodizing process for aluminum materials
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
DE102004021926A1 (en) * 2004-05-04 2005-12-01 Mtu Aero Engines Gmbh A method of making a coating and anode for use in such a method
US20050284766A1 (en) * 2004-06-25 2005-12-29 Herdman Roderick D Pulse reverse electrolysis of acidic copper electroplating solutions
WO2006082218A1 (en) * 2005-02-04 2006-08-10 Siemens Aktiengesellschaft Surface comprising a microstructure that reduces wettability and method for the production thereof
DE102005022692A1 (en) * 2005-05-18 2006-11-23 Robert Bosch Gmbh Process for the preparation of coated surfaces and use thereof
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
DE102008040354A1 (en) 2008-07-11 2010-01-14 Robert Bosch Gmbh High pressure pump for use in common rail system to inject fuel into internal combustion engine, has micro recesses attached in roller shoe surface such that component pair has reduced frictional coefficient than another component pair
EP2149447A1 (en) 2008-07-29 2010-02-03 Alcan Technology &amp; Management Ltd. Method for producing a sheet of material with surface structure
DE102014005941A1 (en) * 2014-04-24 2015-11-12 Te Connectivity Germany Gmbh Method for producing an electrical contact element for avoiding tin whisker formation, and contact element
EP3000918B1 (en) 2014-09-24 2018-10-24 topocrom systems AG Method and device for the galvanic application of a surface coating

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3318786A (en) * 1964-10-16 1967-05-09 Diamond Alkali Co Chromium plating
DE1421984A1 (en) * 1962-10-01 1968-11-07 Forsch Edelmetalle Und Metallc A process for preparing crack-free Chromueberzuegen
US4869971A (en) * 1986-05-22 1989-09-26 Nee Chin Cheng Multilayer pulsed-current electrodeposition process

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2030295A1 (en) * 1970-06-19 1972-01-27 Bosch Gmbh Robert Decorative micropore chromium coating - electroplated on bright and
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

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1421984A1 (en) * 1962-10-01 1968-11-07 Forsch Edelmetalle Und Metallc A process for preparing crack-free Chromueberzuegen
US3318786A (en) * 1964-10-16 1967-05-09 Diamond Alkali Co Chromium plating
US4869971A (en) * 1986-05-22 1989-09-26 Nee Chin Cheng Multilayer pulsed-current electrodeposition process

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 8, no. 102 (C-222)(1539) 12. Mai 1984 & JP-A-59 016 993 ( NIHON EREKUTOROPUREITEINGU ENGINEERS K.K ) 28. Januar 1984 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3438330A1 (en) 2017-08-03 2019-02-06 Groz-Beckert KG Textile machine component and method for producing a textile tool
WO2019025203A1 (en) 2017-08-03 2019-02-07 Groz-Beckert Kommanditgesellschaft Textile machine tool part and method for producing a textile tool

Also Published As

Publication number Publication date
US5415761A (en) 1995-05-16
AT156201T (en) 1997-08-15
DE4211881A1 (en) 1993-10-14
DE4211881C2 (en) 1994-07-28
EP0565070B1 (en) 1997-07-30

Similar Documents

Publication Publication Date Title
US20190145016A1 (en) Methods for producing alloy deposits and controlling the nanostructure thereof using negative current pulsing electro-deposition, and articles incorporating such deposits
US20180163314A1 (en) Coated articles and methods
JP6243381B2 (en) Electrodeposited alloy and its manufacturing method using power pulse
CA2490464C (en) Process for electroplating metallic and metall matrix composite foils, coatings and microcomponents
US6071398A (en) Programmed pulse electroplating process
Peeters et al. Properties of electroless and electroplated Ni–P and its application in microgalvanics
JP2015042789A (en) Method for implementation of nanocrystalline and amorphous metal and alloy thereof as coating
DK172937B1 (en) Galvanic process for forming coatings of nickel, cobalt, nickel alloys or cobalt alloys
US5681443A (en) Method for forming printed circuits
US4652348A (en) Method for the production of alloys possessing high elastic modulus and improved magnetic properties by electrodeposition
Popoola et al. Comparative studies of microstructural, tribological and corrosion properties of plated Zn and Zn-alloy coatings
US5215646A (en) Low profile copper foil and process and apparatus for making bondable metal foils
CN101302644B (en) Method and system for plating workpieces
US3573175A (en) Method of stopping-off plating in electroplating baths
Donten et al. Electrodeposition of amorphous/nanocrystalline and polycrystalline Ni–Mo alloys from pyrophosphate baths
US3706650A (en) Contour activating device
US2451341A (en) Electroplating
US3762882A (en) Wear resistant diamond coating and method of application
Dennis et al. Nickel and chromium plating
US8062496B2 (en) Electroplating method and apparatus
US6942781B2 (en) Method for electroplating a strip of foam
Susan et al. Electrodeposited NiAl particle composite coatings
JP4373923B2 (en) Method for producing structured hard chromium layer
US4673468A (en) Commercial nickel phosphorus electroplating
US10100423B2 (en) Electrodeposition of chromium from trivalent chromium using modulated electric fields

Legal Events

Date Code Title Description
AK Designated contracting states:

Kind code of ref document: A1

Designated state(s): AT CH FR GB IT LI

17P Request for examination filed

Effective date: 19930407

GBC Gb: translation of claims filed (gb section 78(7)/1977)
17Q First examination report

Effective date: 19950515

REF Corresponds to:

Ref document number: 156201

Country of ref document: AT

Date of ref document: 19970815

Kind code of ref document: T

AK Designated contracting states:

Kind code of ref document: B1

Designated state(s): AT CH FR GB IT LI

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

ITF It: translation for a ep patent filed

Owner name: PROROGA CONCESSA IN DATA: 16.12.97;STUDIO JAUMANN

ET Fr: translation filed
GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19971021

26N No opposition filed
REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PGFP Postgrant: annual fees paid to national office

Ref country code: IT

Payment date: 20100419

Year of fee payment: 18

PGFP Postgrant: annual fees paid to national office

Ref country code: FR

Payment date: 20110426

Year of fee payment: 19

PGFP Postgrant: annual fees paid to national office

Ref country code: GB

Payment date: 20110406

Year of fee payment: 19

PG25 Lapsed in a contracting state announced via postgrant inform. from nat. office to epo

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110407

PGFP Postgrant: annual fees paid to national office

Ref country code: CH

Payment date: 20120424

Year of fee payment: 20

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20120407

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20121228

PG25 Lapsed in a contracting state announced via postgrant inform. from nat. office to epo

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120407

PG25 Lapsed in a contracting state announced via postgrant inform. from nat. office to epo

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120430

PGFP Postgrant: annual fees paid to national office

Ref country code: AT

Payment date: 20120426

Year of fee payment: 20

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK07

Ref document number: 156201

Country of ref document: AT

Kind code of ref document: T

Effective date: 20130407