EP0066347B1 - Electrolytic bath for the deposition and penetration of metallic coatings on metallic substrates - Google Patents

Electrolytic bath for the deposition and penetration of metallic coatings on metallic substrates Download PDF

Info

Publication number
EP0066347B1
EP0066347B1 EP82300140A EP82300140A EP0066347B1 EP 0066347 B1 EP0066347 B1 EP 0066347B1 EP 82300140 A EP82300140 A EP 82300140A EP 82300140 A EP82300140 A EP 82300140A EP 0066347 B1 EP0066347 B1 EP 0066347B1
Authority
EP
European Patent Office
Prior art keywords
solution
compound
metal
sem
matrix
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.)
Expired
Application number
EP82300140A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0066347A1 (en
Inventor
Ady Joseph
Lily Mayer
Alexander Miutell
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.)
Metafuse Ltd
Original Assignee
Metafuse Ltd
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 claimed from US06/335,282 external-priority patent/US4566992A/en
Application filed by Metafuse Ltd filed Critical Metafuse Ltd
Priority to AT82300140T priority Critical patent/ATE26596T1/de
Publication of EP0066347A1 publication Critical patent/EP0066347A1/en
Application granted granted Critical
Publication of EP0066347B1 publication Critical patent/EP0066347B1/en
Expired legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/10—Electrodes, e.g. composition, counter electrode
    • C25D17/14—Electrodes, e.g. composition, counter electrode for pad-plating
    • 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
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/623—Porosity of the 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S204/00—Chemistry: electrical and wave energy
    • Y10S204/09—Wave forms

Definitions

  • the present invention is concerned with certain novel solutions which are particularly useful for bonding one material to another, notably one metal to another, according to the process described and claimed in our co-pending Applications filed herewith.
  • a process is described and claimed in our co-pending Application EP-A-56331 for the fusion, at an ambient temperature, of at least one second conductive element comprising ferrous or non-ferrous metals or alloys thereof into a matrix of a first conductive element comprising a ferrous or non-ferrous metal or alloys thereof, said process comprising the steps of
  • the solution of the second material may be aqueous or organic.
  • an aqueous solution is used which has a pH of 0.4 to 14.
  • Both the first and second materials are metal, for example, the first material may be iron or iron alloy and the second material may be molybdenum tungsten or indium. A wide variety of ferrous and/or non-ferrous combinations are contemplated.
  • the said process contemplates the use of a solution containing the metal to be fused (hereinafter the "second metal”) to another metal (hereinafter called the "first metal”), it being understood that the term “metal” is intended to embrace metal alloys as well as single metals.
  • Solutions for plating a metal onto a substrate are known from US-A-3802854 and CH-A-464639.
  • Certain of these solutions may include a sufficient quantity of an organic solvent to ensure dissolution of the metal and/or the complex.
  • Certain other solutions may require conductivity enhancing agents. And depending upon the end result desired, brightening agents may also be present. Wetting agents or surfactants may also be provided.
  • One side of the oscillator output is connected to an electrode 13 through a holder 12.
  • Holder 12 is provided with a rotating chuck and has a trigger switch which controls the speed of rotation of the electrode 13.
  • the speed of rotation is variable from 5,000 to 10,000 rpm.
  • the electrode 13 is composed of the material to be fused with the matrix.
  • the matrix or substrate which is to be subjected to the process and which is to be treated is indicated at 14.
  • the matrix is also connected to the other side of the oscillator output by a clamp 15 and line 16.
  • the electrode is positively charged and the matrix is negatively charged when the signal is applied.
  • the process employed may be characterized as a liquid to solid process.
  • the material to be fused is in the form of a solution and is held in a reservoir 17.
  • Reservoir 17 is connected by a tube 18 to an electrode 19.
  • Electrode 19 is a plate provided with an insulated handle 20 through which one side of oscillator 11 output is connected. This output is led into a main channel 21 in electrode 19.
  • Channel 21 has a series of side channels 22 which open on to the undersurface of electrode 20.
  • the flow from reservoir 17 is by gravity or by a pump and may be controlled by a valve such as 23 on the handle 20.
  • a permeable membrane such as cotton or nylon.
  • the operator passes the rotating electrode 13 in contact with the upper surface of the matrix over the matrix surface at a predetermined speed to apply the electrode material to the matrix and fuse it therewith.
  • both the matrix and the material to be applied have specific resistance characteristics. Thus with each change in either one or both of these materials there is a change in the resistivity of the circuit.
  • a signal having an amplitude of 3 amps is believed to be the preferred amplitude. If the amplitude is greater decarbonizing or burning of the matrix takes place and below this amplitude hydroxides are formed in the interface.
  • FIG. 4 is a schematic diagram of an oscillator circuit used in apparatus in accordance with the present invention.
  • a power supply 30 is connected across the input, and across the input a capacitor 31 is connected.
  • One side of the capacitor 31 is connected through the LC circuit 32 which comprises a variable inductance coil 33 and capacitor 34 connected in parallel.
  • LC circuit 32 is connected to one side of a crystal oscillator circuit comprising crystal 35, inductance 36, NPN transistor 37 and the RC circuit comprised of variable resistance 38 and capacitance 39.
  • This oscillator circuit is connected to output 50 through, on one side capacitor 40, and on the other side diode 41, to produce a halfwave signal across output 50.
  • L and C may be determined by any well-known method.
  • F a depends on the material being treated and the material being applied but it is in the range 400Hz-35MHz. The frequency, it is believed, will determine the speed of the process.
  • the travel speed may be determined by the following form:
  • the speed of rotation is also believed to affect the quality of the fusion with a rotation speed of 5,000 rpm the finish is an uneven 200 to 300 finish; with a speed of rotation of 10,000 rpm the finish is a substantially 15 finish.
  • the apparatus of Figure 2 is operated in the same manner as the apparatus of Figure 1 and the process is essentially the same except for the use of a liquid with a solid electrode.
  • the matrix 14 metal was connected into the circuit as previously described.
  • the frequency was determined in accordance with the formula previously set forth and the solution in reservoir 17 applied by movement of the electrode over one surface of the first metal for varying periods of time as determined by Form II.
  • the electrode was covered with cotton gauze or nylon. It will be apparent that other materials may be employed. This arrangement also served to limit contamination of the solution when graphite electrodes were employed. They had a tendency to release graphite particles in the course of movement.
  • the sample was etched using Nital for steel, the ferrous substrate, and Ammonium Hydrogen Peroxide on the copper, the non-ferrous substrate.
  • a semiquantitative electron probe microanalysis of fused interfaces were performed using an Energy Dispersive X-Ray Spectroscopy (EDX) and a Scanning Electron Microscope (SEM).
  • EDX Energy Dispersive X-Ray Spectroscopy
  • SEM Scanning Electron Microscope
  • the surface of the embedding plastic was rendered conductive by evaporating on it approximately 20 ⁇ m layer of carbon in a vacuum evaporator. This procedure was used to prevent buildup of electrical charges on an otherwise nonconductive material and a consequent instability of the SEM image. Carbon, which does not produce a radiation detectable by the EDX, was used in preference of a more conventional metallic coating to avoid interference of such a coating with the elemental analysis.
  • the diameter of analysed volume was calculated for typical elements analysed and was found to be as follows:
  • these solutions are aqueous, have a pH of about 0.4-14, a resistivity of 10 to 80 ohms cm and contain:
  • Certain of these solutions may include a sufficient quantity of an organic solvent to ensure dissolution of the metal and/or the complex.
  • Certain other solutions may require conductivity enhancing agents. And depending upon the end result desired, brightening agents may also be present. Wetting agents or surfactants may also be provided.
  • a variety of dissociable polyvalent metal compounds may be used as component (1) provided they are soluble in the solution medium.
  • Typical compounds include: sodium molybdate, sodium tungstate, indium sulphate, nickelous sulphate, nickelous chloride, chloroauric acid, chromium trioxide, chromium sulphate, chromic chloride, cadmium chloride, cadmium sulphate, stannous chloride, cobaltous sulphate, silver cyanide, silver nitrate.
  • Normally component (1) will be used in an amount varying from 0.10 to 10% by weight based on the total weight of the solution.
  • Representative metal complexing agents useful as component (2) include, such as, pyrophosphates, ethylene diamine tetracetic acid, citric acid, and potassium iodide and the like.
  • pyrophosphates also serve as stabilizing agents.
  • This component will usually consist of from 3 to 10% of the weight of solution. However, the amount can be varied and should be selected to give optimum complexing with (1).
  • stabilizers and catalysts may be used as components (3) and (4), respectively.
  • Typical stabilizers are the following: boric acid, citric acid or citrates, pyrophosphates, acetates and aluminum sulphate; while suitable catalysts include: metallic ions such as iron, nickel, antimony, and zinc, and organic compounds such as dextrine, hydroquinone, gelatin, pepsin and acacia gum.
  • Typical acids, and bases include the following:
  • Bases ammonium hydroxide, sodium hydroxide, potassium hydroxide and basic salts such as alkali carbonates and bicarbonates.
  • Typical brighteners are formaldehyde and carbon disulphide.
  • a surfactant or wetting agent which is employed in some solutions is sodium lauryl sulphate. Others familiar to those in the art may be substituted.
  • a conductivity enhancing agent such as sodium sulphate may be employed.
  • second chemical conductive element complexing agents which preclude precipitation of the second element.
  • These agents were by way of example citric acid, or sodium pyrophosphate, or ethyldiaminetetracetic acid or their equivalents.
  • a suitable buffer is also provided in certain solutions, where required.
  • the water is always demineralized.
  • AtfasA151 1020 steel was connected in the apparatus of Figure 2 as the matrix 14 and a 10% solution of ammonium molybdate in water was placed in reservoir 17.
  • Example I The sample of Example I was subject to a thermal corrosion test. 25% sulphuric acid was applied to the surface for 20 minutes at 325°C without any surface penetration.
  • the Mo +6 concentration may be varied from 1.5% to 2.5% by weight; the pH from 7.2 to 8.2 and the resistivity from 17-25 ohms cm.
  • the photomicrograph Figure 7 shows the deposition of a substantially uniform layer of molybdenum 1 micron thick of uniform density.
  • an SEM/EPMA scan across the interface between the substrate and the applied metal shows molybdenum was present to a depth of at least 10 microns and a molybdenum gradient as set out below in Table.
  • the W +6 concentration may vary from 1.6% to 2.5%; the pH may vary from 7.5 to 8.5; and the resistivity may vary from 18 ohms cm to 24 ohms cm.
  • the sample showed a uniform deposit of tungsten approximately 1 micron thick.
  • An SEM/EPMA scan showed fusion of tungsten on copper to a depth of at least 5.0 microns, as can be seen in the Table below and Figure 11.
  • the concentration of tungsten may be varied from 1.6% to 2.5% by wt.; the pH from 7.5 to 8.5; and the conductivity from 18.8 ohms cm to 22.8 ohms cm.
  • the Indium concentration may vary from 0.2% to 2.2%; the pH from 1.60 to 1.68; and the resistivity from 48.8 ohms cm to 54.8 ohms cm. Reaction conditions
  • Example VI The solution of Example VI was employed and applied to a steel matrix:
  • Figure 18 shows a solid deposit of nickel of uniform density approximately 1.5 pm thick. As shown in the following Table and Figure 19 an SEM/EPMA scan across the interface between the matrix and the nickel layer shows nickel to be fused to a depth of at least 4 ⁇ m.
  • the nickel concentration may vary from 2% to 10%; pH from 3.10 to 3.50; and resistivity from 17 ohms cm to 26 ohms cm.
  • Example X The same solution as was formulated for Example X was prepared and applied to a steel matrix:
  • the nickel layer is continuous and substantially uniform in thickness being about 1.5 ⁇ m thick.
  • nickel is shown to be fused to a depth of at least 3 ⁇ m.
  • the pH may be varied from 3.70 to 11; the concentration of Au +3 ions may vary from 0.1 % to 0.5% by weight; and the resistivity from 40 ohms cm to 72 ohms cm.
  • An SEM/EPMA scan across the interface indicated fusion of gold to a depth of at least 3 ⁇ m as shown on the Table below and Figure 23.
  • An SEM/EPMA scan across the interface indicated fusion of gold to a depth of at least 4.0 ⁇ m as shown on the table below and Figure 25.
  • the pH may be varied from 0.6 to 1.0; the concentration of Cr +6 ions may vary from 3% to 20% by weight; and the resistivity from 11 ohms cm to 14 ohms cm.
  • An SEM/EPMA scan across the interface indicated fusion of chromium to a depth of at least 3.0 ⁇ m as shown on the table below and Figure 27.
  • An SEM/EPMA scan across the interface indicated fusion of chromium to a depth of at least 5.0 ⁇ m as shown on the table below and Figure 29.
  • the pH may be varied from 2.5 to 3.5; the concentration of Cr +3 ions may vary from 1.8% to 5% by weight; and the resistivity from 16 ohms cm to 20 ohms cm.
  • An SEM/EPMA scan across the interface indicated fusion of chromium to a depth of at least 3.0 ⁇ m as shown on the Table below and Figure 32.
  • An SEM/EPMA scan across the interface indicated fusion of chromium to a depth of at least 3.0 ⁇ m as shown on the table below and Figure 34.
  • the pH may be varied from 10 to 10.2; the concentration of Cd +2 ions may vary from 0.2% to 0.5% by weight; and the resistivity from 28 ohms cm to 35 ohms cm.
  • Example XVII Example XVII
  • the pH may be varied from 3.2 to 3.5; the concentration of Cd +2 ions may vary from 1% to 4% by weight; and the resistivity from 45 ohms cm to 55 ohms cm.
  • the pH may be varied from 11.2 to 12.7; the concentration of Sn +2 ions may vary from 2% to 5% by weight; and the resistivity from 6.2 ohms cm to 10.3 ohms cm.
  • An SEM/EPMA scan across the interface indicated fusion of tin to a depth of at least 4 ⁇ m as shown on the table below and Figure 40.
  • the pH may be varied from 9 to 9.7; the concentration of Sn +2 ions may vary from 0.4% to 1% by weight; and the resistivity from 30 ohms cm to 36 ohms cm.
  • This deposit appears to comprise a lower uniform and substantially homogeneous layer of approximately 1 ⁇ m thick and an outer slightly porous layer approximately 3 ⁇ m thick as shown in Figure 41.
  • An SEM/EPMA scan across the interface indicated fusion of tin to a depth of at least 2 ⁇ m as shown on the table below and Figure 44.
  • the pH may be varied from 4.5 to 6.5; the concentration of Co +2 ions may vary from 2% to 6% by weight; and the resistivity from 25 ohms cm to 30 ohms cm.
  • the pH may be varied from 11.2 to 11.7; the concentration of Ag +1 ions may vary from 1% to 3% by weight; and the resistivity from 8 ohms cm to 13 ohms cm.
  • An SEM/EPMA scan across the interface indicated fusion of silver to a depth of at least 3 pm as shown on the Table below and Figure 48.
  • the pH may be varied from 1.5 to 2; the concentration of Ag +1 ions may vary from 0.5% to 2.5% by weight; and the resistivity from 6 ohms cm to 12 ohms cm.
  • An SEM/EPMA scan across the interface indicated fusion of silver to a depth of at least 2.00 Il m as shown on the Table below and Figure 50.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemically Coating (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Catalysts (AREA)
  • Oscillators With Electromechanical Resonators (AREA)
EP82300140A 1981-01-13 1982-01-12 Electrolytic bath for the deposition and penetration of metallic coatings on metallic substrates Expired EP0066347B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT82300140T ATE26596T1 (de) 1981-01-13 1982-01-12 Elektrolysebad zur abscheidung und verbindung metallischer ueberzuege auf metallischen substraten.

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US22476281A 1981-01-13 1981-01-13
US224762 1981-01-13
US31967281A 1981-11-09 1981-11-09
US06/335,282 US4566992A (en) 1981-12-28 1981-12-28 Solutions for the fusion of one metal to another
US319672 1994-10-12
US335282 1994-11-07

Publications (2)

Publication Number Publication Date
EP0066347A1 EP0066347A1 (en) 1982-12-08
EP0066347B1 true EP0066347B1 (en) 1987-04-15

Family

ID=27397402

Family Applications (1)

Application Number Title Priority Date Filing Date
EP82300140A Expired EP0066347B1 (en) 1981-01-13 1982-01-12 Electrolytic bath for the deposition and penetration of metallic coatings on metallic substrates

Country Status (8)

Country Link
EP (1) EP0066347B1 (da)
KR (1) KR830009258A (da)
AU (1) AU7944982A (da)
DD (1) DD202313A5 (da)
DE (1) DE3276074D1 (da)
DK (1) DK11182A (da)
FI (1) FI820081L (da)
NO (1) NO820076L (da)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6200529B1 (en) * 1998-12-31 2001-03-13 A. S. Incorporated Corrosion inhibition method suitable for use in potable water
US6416712B2 (en) 1998-12-31 2002-07-09 A.S. Incorporated Corrosion inhibition method suitable for use in potable water
CA3048786C (en) * 2010-09-24 2020-11-03 Dnv Gl As Method and apparatus for the electrochemical reduction of carbon dioxide
CN103469460B (zh) * 2013-09-10 2014-12-24 江苏金龙科技股份有限公司 电脑针织横编机的纱线张力调整装置

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH464639A (de) * 1964-11-21 1968-10-31 Bobst Joseph Verfahren zur Herstellung metallischer Tantal- oder Niobüberzüge durch Elektrolyse aus wässriger Lösung
US3802854A (en) * 1973-03-19 1974-04-09 Akad Wissenschaften Ddr Process for forming magnetic metal deposits on a flexible base for use as information data carrier product thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Kuhn: Industrial Electrochemical Processes N.Y. (1971) Elseres Publ. p. 354/55 *

Also Published As

Publication number Publication date
KR830009258A (ko) 1983-12-19
DD202313A5 (de) 1983-09-07
DK11182A (da) 1982-07-14
EP0066347A1 (en) 1982-12-08
DE3276074D1 (en) 1987-05-21
AU7944982A (en) 1982-07-22
FI820081L (fi) 1982-07-14
NO820076L (no) 1982-07-14

Similar Documents

Publication Publication Date Title
US6406611B1 (en) Nickel cobalt phosphorous low stress electroplating
KR0184889B1 (ko) 산성 팔라듐 스트라이크욕
US5190796A (en) Method of applying metal coatings on diamond and articles made therefrom
JP2002515090A (ja) 非晶質で微晶質のニッケル−タングステン被膜の電着
KR20140117669A (ko) 코팅 물품 및 방법
Zhang Tin and tin alloys for lead-free solder
US20120070688A1 (en) Coated articles and methods
JP5872492B2 (ja) 被覆物および方法
MX2010012956A (es) Material metalico con pelicula de bismuto adherida y metodo para producir el mismo, tratamiento superficial utilizado en el metodo, y material metalico recubierto por electrodeposicion cationica y metodo para producir el mismo.
Valova et al. Electroless deposited Ni–Re–P, Ni–W–P and Ni–Re–W–P alloys
EP0066347B1 (en) Electrolytic bath for the deposition and penetration of metallic coatings on metallic substrates
US6281157B1 (en) Self-catalytic bath and method for the deposition of a nickel-phosphorus alloy on a substrate
EP2755819B1 (en) Silver alloy coated articles
MX2013003935A (es) Proceso para deposicion por via quimica de metales utilizando baño de chapado altamente alcalino.
US4566992A (en) Solutions for the fusion of one metal to another
Makrides Kinetics of the Fe+++/Fe++ Reaction on Fe‐Cr Alloys
EP0056331B1 (en) Process and apparatus for treating electrically conductive matrices and products produced by the process
US4840711A (en) Process for the fusion of one element into a second element
US4764654A (en) Process and apparatus for treating electrically conductive matrices and products produced by the process
CA1220160A (en) Solutions for the fusion of one metal to another
StankeviČiu¯ tĖ et al. Deposition of Zn–Co by constant and pulsed current
EP0057505B1 (en) Process and apparatus for treating electrically conductive matrices, solutions for use in such a process, and products thereof
JPS6140316B2 (da)
US3445351A (en) Process for plating metals
WO2002063070A1 (en) Nickel cobalt phosphorous low stress electroplating

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): AT BE CH DE FR GB IT NL SE

17P Request for examination filed

Effective date: 19830808

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE FR GB IT LI NL SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19870415

Ref country code: LI

Effective date: 19870415

Ref country code: CH

Effective date: 19870415

Ref country code: AT

Effective date: 19870415

REF Corresponds to:

Ref document number: 26596

Country of ref document: AT

Date of ref document: 19870515

Kind code of ref document: T

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19870430

REF Corresponds to:

Ref document number: 3276074

Country of ref document: DE

Date of ref document: 19870521

ITF It: translation for a ep patent filed

Owner name: JACOBACCI & PERANI S.P.A.

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

ET Fr: translation filed
NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19890731

Year of fee payment: 8

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Effective date: 19900131

BERE Be: lapsed

Owner name: METAFUSE LTD

Effective date: 19900131

ITTA It: last paid annual fee
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19910704

Year of fee payment: 10

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19920930

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: FR

Ref legal event code: AR

REG Reference to a national code

Ref country code: FR

Ref legal event code: DI

REG Reference to a national code

Ref country code: FR

Ref legal event code: JE

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19950306

Year of fee payment: 14

Ref country code: DE

Payment date: 19950306

Year of fee payment: 14

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19960112

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

Effective date: 19960112

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19961001