EP0448888A1 - Verfahren zur galvanischen Behandlung mit gepulstem Strom - Google Patents

Verfahren zur galvanischen Behandlung mit gepulstem Strom Download PDF

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Publication number
EP0448888A1
EP0448888A1 EP90400825A EP90400825A EP0448888A1 EP 0448888 A1 EP0448888 A1 EP 0448888A1 EP 90400825 A EP90400825 A EP 90400825A EP 90400825 A EP90400825 A EP 90400825A EP 0448888 A1 EP0448888 A1 EP 0448888A1
Authority
EP
European Patent Office
Prior art keywords
current
pulsed
nickel
time
galvanic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP90400825A
Other languages
English (en)
French (fr)
Inventor
Michel Panza
Pascal Panza
Paul Buricand
Christine Girodie
Rémi Willmotte
Guy Joly
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.)
ETS MICHEL SA
Original Assignee
ETS MICHEL SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ETS MICHEL SA filed Critical ETS MICHEL SA
Priority to EP90400825A priority Critical patent/EP0448888A1/de
Priority to MA22367A priority patent/MA22090A1/fr
Priority to PT97141A priority patent/PT97141A/pt
Priority to TNTNSN91018A priority patent/TNSN91018A1/fr
Priority to CA002039106A priority patent/CA2039106A1/en
Publication of EP0448888A1 publication Critical patent/EP0448888A1/de
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C25D1/00—Electroforming
    • C25D1/08—Perforated or foraminous objects, e.g. sieves
    • 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
    • C25D5/615—Microstructure of the layers, e.g. mixed structure
    • C25D5/617—Crystalline layers

Definitions

  • the present invention relates to galvanic treatment by depositing nickel alone or with other metals. It relates more particularly to the production of rotary stencils for textile printing, and in general to the galvanic treatment of parts comprising recesses of reduced size, of the order of 100 to 400 micrometers.
  • the engraved stencil is conventionally produced by direct current electroplating. From the drawing that we want to print, we make a screened negative film. We postpone the screened drawing by exposure of the film on a photosensitive coating covering a roller, which acts as the matrix of the stencil to be manufactured. After exposure and development, the coating corresponding to the unexposed areas is dissolved.
  • the matrix playing the role of cathode is placed in the galvanic bath, for example with nickel sulfamate at a rate of 250 to 450 g / l.
  • the nickel deposition takes place regularly on the external surface of the matrix; the zones corresponding to the insulating coating form the screening points in the depot.
  • the cylinder consisting of the nickel deposit is then peeled off from the matrix and constitutes the stencil.
  • the thickness of the nickel deposit is greater than that of the coating, it can be seen that the deposit takes on a conical shape at the periphery of the screening points, tending to block the point orifice.
  • the shutter rate or blockage coefficient is at least 35%.
  • the galvanic method uses pulsed currents whose imposition time of the cathode current (Tc) is between 0.1 and 10 ms.
  • the pulsed currents used are for example simple pulsed currents having a rest time (Tr) between 1 and 15 ms and a current density of the cathode peak between 4 and 30A / dm2.
  • the shutter rate is at most 30%, which constitutes a significant improvement.
  • the shutter rate can be reduced considerably, by using reverse pulsed currents having a rest time of less than 10 ms, an imposition time of the anode current (Ta) of between 0.5 and 10 ms, a current density of the cathode peak between 4 and 40A / dm2 and a current density of the anode peak between 1 and 20A / dm2.
  • This performance could be due to a particularly rapid discharge of the double electrical layer in the vicinity of the cathode.
  • the shutter rate is at most 25%.
  • the galvanic bath comprises from 550 to 600 mg / l of nickel sulfamate.
  • a screened negative film 1 is made, according to the well-known screening technique.
  • Screened negative 1 shown in Figure 1A has areas opaque 2 which delimit transparent areas 3; these are the transparent zones 3 which correspond to the drawing to be printed in the case of a stencil for printing, in particular textile.
  • the screened negative 1 is placed above a matrix 4, the outer surface of which is coated with a photosensitive coating 5.
  • the matrix 4 is a roller in the case of a rotary stencil.
  • the matrix 4 / prominence 6 assembly is placed in a galvanic bath based on nickel sulfamate.
  • the matrix 6 plays the role of cathode.
  • a nickel deposit 7 is first formed uniformly on the surface of the matrix, surrounding the prominences 6, then, when the thickness of the deposit increases beyond the thickness of the prominences, the deposit has holes 8 at the level of said prominences 6; these holes 8 constitute the screening points (FIG. 1C). When its thickness is sufficient, the deposit 7 is detached from the matrix 4 and forms the stencil (FIG. 1D).
  • the points 8 do not have vertical and regular walls 9, but that these walls 9 have a conical shape which tends to partially block the recess due to the presence of a prominence 6.
  • the shutter rate or plugging coefficient corresponds to the part of the initial recess which is occupied by the conical protuberances of the deposit. It is understood that when the recesses are intended to contain a printing fluid, this plugging phenomenon is a handicap.
  • the current used during the galvanic treatment is not a direct current, but a pulsed current whose imposition time of the cathode current is between 0.1 and 10 ms.
  • FIG. 2 shows the current density / time curve of a simple pulsed current.
  • a current of this type is characterized by its period T which decomposes in a time imposition of the cathode current Tc and in a rest time Tr, and by the current density of the cathode peak Jc.
  • FIG. 3 shows the potential / time transient curve in response to a square current pulse.
  • the variation of the potential during the time Tc of imposition of the cathode current occurs in several distinct stages.
  • the first step is almost instantaneous; it corresponds to the charge of the electrochemical double layer in the vicinity of the cathode, from the potential Vo at the initial time To to the potential V1.
  • the second stage corresponds to the faradic level, the potential remaining constant.
  • the third stage which expires with time Tc, the potential gradually increases until V2.
  • the fourth step which begins with the rest time Tr, corresponds to the discharge of the electrochemical double layer.
  • the electroplating of nickel takes place under different conditions depending on whether one is in the second, third or fourth stage, and that the plugging phenomenon occurs for the deposits made preferentially during the third and fourth stages.
  • the choice of the imposition time of the cathode current between 0.1 and 10 ms, aims to reduce the overall diffusion time while retaining the faradic plateau.
  • a galvanic bath having the following approximate composition: nickel sulfamate of 550 to 600 g / l, nickel chloride of 5 to 15 g / l, boric acid of 30 to 40 g / l, the pH being between 3.5 and 4.5; the temperature between 40 and 70 ° C.
  • the anodes were made of electrolytic nickel or sulfur depolarized nickel.
  • Benzoic O-sulfimide was added as a ductilizer, and to facilitate the demolding of 2 butyne 1-4 diol, at a rate of a few mg / l.
  • a stencil was made having a thickness of 90 micrometers. The obturation rate observed was 30%.
  • the pulsed current was an inverted pulsed current, of the type shown in FIG. 4, in which the time of imposition of the cathode current Tc is immediately followed by an anode inversion for a time Ta.
  • a stencil was made having a thickness of 90 micrometers. The obturation rate observed was 20%.
  • the invention is not limited to the embodiments which have been described by way of example but covers all the variants thereof.
  • the invention is not limited to the deposition of nickel alone, but also relates to the deposition of nickel in admixture with other metals, for example cobalt or tungsten.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Printing Plates And Materials Therefor (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Catalysts (AREA)
EP90400825A 1990-03-27 1990-03-27 Verfahren zur galvanischen Behandlung mit gepulstem Strom Withdrawn EP0448888A1 (de)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP90400825A EP0448888A1 (de) 1990-03-27 1990-03-27 Verfahren zur galvanischen Behandlung mit gepulstem Strom
MA22367A MA22090A1 (fr) 1990-03-27 1991-03-25 Procede de traitement galvanique par courants pulses.
PT97141A PT97141A (pt) 1990-03-27 1991-03-26 Processo de tratamento galvanico atraves de correntes pulsadas
TNTNSN91018A TNSN91018A1 (fr) 1990-03-27 1991-03-26 Procede de traitement galvanique par courants pulses
CA002039106A CA2039106A1 (en) 1990-03-27 1991-03-26 Process of galvanic treatment by pulsed currents

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP90400825A EP0448888A1 (de) 1990-03-27 1990-03-27 Verfahren zur galvanischen Behandlung mit gepulstem Strom

Publications (1)

Publication Number Publication Date
EP0448888A1 true EP0448888A1 (de) 1991-10-02

Family

ID=8205693

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90400825A Withdrawn EP0448888A1 (de) 1990-03-27 1990-03-27 Verfahren zur galvanischen Behandlung mit gepulstem Strom

Country Status (5)

Country Link
EP (1) EP0448888A1 (de)
CA (1) CA2039106A1 (de)
MA (1) MA22090A1 (de)
PT (1) PT97141A (de)
TN (1) TNSN91018A1 (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10259362A1 (de) * 2002-12-18 2004-07-08 Siemens Ag Verfahren zum Abscheiden einer Legierung auf ein Substrat
WO2004067806A1 (en) * 2003-01-31 2004-08-12 Microstencil Limited Stencil manufacture

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0038104A1 (de) * 1980-04-15 1981-10-21 Stork Screens B.V. Verfahren zur elektrolytischen Herstellung eines Siebes, sowie ein unter Anwendung dieses Verfahrens hergestelltes Sieb
EP0079642A1 (de) * 1981-11-13 1983-05-25 Stork Veco B.V. Verfahren und Vorrichtung zum galvanoplastischen Herstellen von Sieben, sowie damit hergestellte Siebe

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0038104A1 (de) * 1980-04-15 1981-10-21 Stork Screens B.V. Verfahren zur elektrolytischen Herstellung eines Siebes, sowie ein unter Anwendung dieses Verfahrens hergestelltes Sieb
EP0079642A1 (de) * 1981-11-13 1983-05-25 Stork Veco B.V. Verfahren und Vorrichtung zum galvanoplastischen Herstellen von Sieben, sowie damit hergestellte Siebe

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
J.K. DENNIS et al.: "Nickel and Chromium Plating", 1972, pages 60-61, Newnes-Butterworths, London, GB *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10259362A1 (de) * 2002-12-18 2004-07-08 Siemens Ag Verfahren zum Abscheiden einer Legierung auf ein Substrat
WO2004067806A1 (en) * 2003-01-31 2004-08-12 Microstencil Limited Stencil manufacture
JP2006518808A (ja) * 2003-01-31 2006-08-17 マイクロステンシル リミテッド ステンシル製造方法

Also Published As

Publication number Publication date
TNSN91018A1 (fr) 1992-10-25
MA22090A1 (fr) 1991-10-01
CA2039106A1 (en) 1991-09-28
PT97141A (pt) 1993-03-31

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