EP0056331B1 - Verfahren und Vorrichtung zur Behandlung elektrisch leitender Materialien und damit erhaltene Produkte - Google Patents

Verfahren und Vorrichtung zur Behandlung elektrisch leitender Materialien und damit erhaltene Produkte Download PDF

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Publication number
EP0056331B1
EP0056331B1 EP82300138A EP82300138A EP0056331B1 EP 0056331 B1 EP0056331 B1 EP 0056331B1 EP 82300138 A EP82300138 A EP 82300138A EP 82300138 A EP82300138 A EP 82300138A EP 0056331 B1 EP0056331 B1 EP 0056331B1
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Prior art keywords
matrix
conductive element
sem
solution
fusion
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EP82300138A
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English (en)
French (fr)
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EP0056331A1 (de
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Joseph Ady
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Metafuse Ltd
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Metafuse Ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C20/00—Chemical coating by decomposition of either solid compounds or suspensions of the coating forming compounds, without leaving reaction products of surface material in the coating
    • 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
    • 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
    • C25D5/60—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

Definitions

  • the present invention relates to fusion processes, apparatus for carrying out such processes and the products of such processes.
  • fusion is employed as meaning a process whereby diverse elements are chemically or physically bonded.
  • the workpiece or matrix may be of a certain form which does not lend itself to the subjection of a particular characteristic-enhancing process;-the process may be destructive of the already desirable characteristics of the work-piece; or the treated work-piece while having certain enhanced characteristics may exhibit other reduced characteristics.
  • the process employed depends upon the work-piece or matrix to be treated and the characteristics desired.
  • coating techniques heat treatment, anodizing, arc spraying, vaccum evaporation, chemical deposition, sputtering, and ion plating are all common processes.
  • Non-ferrous metals may be hardened by aging, heat treatment or anodizing.
  • Spray coating techniques have not improved corrosion resistance or the physical properties of ferrous materials.
  • the other techniques arc-spraying, vaccum evaporation and sputtering have their shortcomings in that the coating deposited is usually thin, the interfacial bond strength is poor, or can only be used to treat small surface areas.
  • U.S. Application No. 3743590 discloses an electroplating device having a continuously rotating anode with a continuous supply of plating solution provided through the anode to provide optimum plating.
  • first conductive element shall refer to the matrix with which fusion is to be accomplished; and the term “chemical element” shall refer to such an element or an alloy thereof; the term “second conductive element or an alloy thereof” shall refer to the element which is to be fused with the matrix.
  • fusion means a penetration by the atoms or molecules of a second element within the solid matrix of a first element or alloy thereof.
  • Solutions for use in the process and in association with the apparatus may comprise a solution of a conductive chemical of the chemical to be fused in a dissociable form which may be present in the range of 0.10% to 10% by weight and having a pH in the range of 0.4 to 14.
  • the resistivity of the solution is in the range of 5 to 500 ohms cm, preferably 10 to 80 ohms cm.
  • 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.
  • the surface of electrode 19 is preferably covered by a permable 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.
  • the travel speed may be determined by the following form:
  • resistances R 1 and R 2 may be measured by any known means.
  • 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 p 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 solid to solid process is illustrated by Examples I, II, IIA, III, and IV.
  • Figures 9, 10 and 11 give spectra from the parent metal.
  • Figures 12 through 16 show the presence of a small titanium peak which does not change markedly in height as the zone was crossed.
  • the approximate width of the zone in which titanium was detected is about 50 m although this dimension varied along the specimen length.
  • 1018 Steel was connected to the apparatus of Figure 1 as the matrix 14 and the electrode 13 was molybdenum, Type Mo 1.
  • the steel was 12.7 mm widex6.35 mm thickx38.1 mm long, the molybdenum 25.4 mm longx4 mm diameter.
  • the frequency applied was 43.31 KHz and the speed of electrode rotation approximately 12,000 rpm.
  • the surface of the steel was ground to a surface finish of 600 grit.
  • the electrode tip was moved manually along the top surface of the steel sample in straight lines adjacent to each other. The process was repeated at 90° to cover the whole surface. Under the optical microscope at x40 magnification small beads of melted and resolidified material were revealed.
  • the average KHN of the untreated steel was 188.
  • the hardness of the same steel after heating to 900°C and water quenching was 285 (KHN) at 200 gm.
  • Example II The same matrix and electrode and procedure as in Example II were followed at a frequency of 30.60 3 KHz and the same speed of rotation.
  • the frequency applied was 26.20 KHz and the speed of electrode rotation was approximately 12,000 rpm.
  • tungsten is shown to be fused with the steel matrix.
  • the results of an electron microscope analysis across the sample indicate the presence of tungsten to a depth of at least 80 pm and are shown in Figure 21 and the following table:
  • the hardness of the untreated sample is approximately 188 KHN and after heating to 900°C and quenching was 285 KHN.
  • 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 pm 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:
  • the second conductive chemical element that is the element to be diffused into the matrix
  • small quantities of metallic ions of a third metal are also provided.
  • the presence of these metal ions is believed to be required as complex forming agents to facilitate fusion.
  • Small quantities of organic catalysts such as gum acacia, hydroquinone, animal glue, pepsin, dextrin, licorice, or their equivalents may also be present.
  • wetting agents such as sodium lauryl sulphate or its equivalent are usually provided.
  • pH varying agents such as ammonium hydroxide or sulphuric acid are usually added to reach an operating pH.
  • 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.
  • Atlas A151 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 IV The sample of Example IV 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 24 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 solution had the following characteristics:
  • 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 28.
  • 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 solution had the following characteristics: 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.
  • Example IX The solution of Example IX was employed and applied to a steel matrix:
  • Figure 35 shows a solid deposit of nickel of uniform density approximately 1.5 pm thick.
  • 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.
  • aqueous solution of the following formulation was prepared: The solution had the following characteristics: 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 XI The same solution as was formulated for Example XI 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.
  • aqueous solution of the following formulation was prepared: This solution had the following characteristics: 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. Observation with the optical and scanning electron microscope revealed a surface deposition of gold approximately 1.5 ⁇ m thick. The deposit was continuous and uniformly dense as shown in Figure 39.
  • 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 40.
  • Example XIII An aqueous solution of the same formulation as that of Example XIII was prepared: Observation with the optical and scanning electron microscope revealed a surface deposition of gold approximately 1.0 ⁇ m thick. The deposit was uniformly thick and dense as shown in Figure 41.
  • 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 42.
  • 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. Observation with the optical and scanning electron microscope revealed a surface deposition of chromium approximately 1 pm thick. The surface of the layer was irregular but the deposit appeared free of faults and was continuous as shown in Figure 43.
  • 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 44.
  • Example XV An aqueous solution of the same formulation as employed in Example XV was prepared: Observation with the optical and scanning electrode microscope revealed a surface deposition of chromium approximately 3.0 ⁇ m thick. This is as shown in Figure 45.
  • 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 46.
  • aqueous solution of the following formulation was prepared: This solution had the following characteristics: 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. Observation with the optical and scanning electron microscope revealed a surface deposition of chromium approximately 0.5 ⁇ m thick. The deposit was solid and continuous as shown in Figures 47 and 47A.
  • An SEM/EPMA scan across the interface indicated fusion of chromium ta a depth of at least 3.0 ⁇ m as shown on the Table below and Figure 48.
  • 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 50.
  • 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.
  • the solution employed was initially as set out above, applied in accordance with the conditions identified as (1).
  • a second solution, that set forth in Example XX, was then applied under the conditions identified as (2).
  • Observation with the optical and scanning electron microscope revealed a surface deposition of cadmium approximately 4 p m thick. This deposit was not homogeneous as shown in Figure 51 but an SEM/EPMA scan across the interface indicated fusion of cadmium to a depth of at least 9 ⁇ m as shown on the Table below and Figure 52.
  • 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 56.
  • 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.
  • An SEM/EPMA scan across the interface indicated fusion of tin to a depth of at least 5 ⁇ m as shown on the Table below and Figure 58.
  • Example XXII An aqueous solution of the same as prepared for Example XXII was employed: Observation with the optical and scanning electron microscope revealed a surface deposition of tin exceeding 2 ⁇ m thick. This layer was porous but continuous as shown in Figure 59.
  • 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.
  • Observation with the optical and scanning electron microscope revealed a surface deposition of cobalt approximately 6.5 pm thick. This layer was uniform and continuous as shown in Figure 61.
  • 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 ⁇ m as shown on the Table below and Figure 64.
  • 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 J.lm as shown on the Table below and Figure 66.
  • tin, gold and silver with their inherent excellent conductivity characteristics may be employed in electrical applications and circuits may be fused on other substrates.
  • the anti-corrosion characteristics of tin, gold, silver, nickel, chromium, cadmium, molybdenum and tungsten are also useful. And the application of those metals to ferrous or non-ferrous substrates will enhance their anti-corrosion behavior.
  • Chromium, nickel, silver, gold or tin have the capability of imparting an elegant appearance to the matrix. Chromium, molybdenum, tungsten, titanium and cobalt impart a surface hardness to the matrix.
  • Indium imparts strength to the matrix, and also serves as anti-galling agent.
  • a molybdenum treated ferrous or non-ferrous matrix has improved friction-wear and high temperature resistance characteristics. It is also useful as a dielectric coating.
  • a cadmium fused matrix as well as having enhanced corrosion resistance characteristics can also serve as an anti-fouling agent for ship hull treatment.
  • Silver fused matrices are all useful as a reflecting medium.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
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  • Electroplating Methods And Accessories (AREA)

Claims (6)

1. Verfahren zum Einschmelzen wenigstens eines zweiten, Eisen- oder Nichteisenmetalle oder Legierungen derselben enthaltenden leitfähigen Elementes in eine Matrix eines ersten, Eisen- oder Nichteisenmetalle oder Legierungen derselben enthaltenden leitfähigen Elementes bei Umgebungstemperatur, wobei
a) das leitfähige Element mit einem begrenzten Bereich einer benachbarten Oberfläche des ersten leitfähigen Elementes in Kontakt gebracht wird,
b) ein Halbwellenimpuls in einem Bereich zwischen 2,5 Microsekunden und 28,6 Nanosekunden mit einer Frequenz zwischen 400 Hz und 35 MHz und einer Amplitude von etwa 3 A über eine Fläche von etwa 0,3 mm2 angelegt wird und
c) das leitfähige Element in das erste leitfähige Element bis auf eine Tiefe von mehr als 0,5 um eingeschmolzen und eine Oberflächenschicht des zweiten chemischen Elementes von mehr als 0,5 um Dicke abgelagert wird.
2. Verfahren nach Anspruch 1, worin das zweite leitfähige Element in der Form einer das zweite leitfähige Element enthaltenden Festkörper-Elektrode vorliegt.
3. Verfahren nach einem der Ansprüche 1 bis 2, dadurch gekennzeichnet, daß das erste leitfähige Element ein Eisenmetall oder eine Legierung daraus und das zweite leitfähige Element ein Nichteisenmetall oder eine Legierung daraus sind.
4. Verfahren nach einem der Ansprüche 1 bis 2, dadurch gekennzeichnet, daß das erste leitfähige Element ein Nichteisenmetall oder eine Legierung daraus und das zweite leitfähige Element ein Eisenmetall oder eine Legierung daraus sind.
5. Verfahren nach einem der Ansprüche 1-4, worin das zweite leitfähige Element mit einer Geschwindigkeit zwischen 5.000 und 10.000 Umdrehungen/min. rotiert wird.
6. Verfahren nach einem der Ansprüche 1, 3 bis 5, dadurch gekennzeichnet, daß das zweite leitfähige Element in flüssiger Form vorliegt.
EP82300138A 1981-01-13 1982-01-12 Verfahren und Vorrichtung zur Behandlung elektrisch leitender Materialien und damit erhaltene Produkte Expired EP0056331B1 (de)

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Application Number Priority Date Filing Date Title
AT82300138T ATE26595T1 (de) 1981-01-13 1982-01-12 Verfahren und vorrichtung zur behandlung elektrisch leitender materialien und damit erhaltene produkte.

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US22476281A 1981-01-13 1981-01-13
US224762 1981-01-13
US31967881A 1981-11-09 1981-11-09
US319678 1981-11-09

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EP0056331A1 EP0056331A1 (de) 1982-07-21
EP0056331B1 true EP0056331B1 (de) 1987-04-15

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EP (1) EP0056331B1 (de)
KR (1) KR830009256A (de)
AU (1) AU7944782A (de)
BR (1) BR8200156A (de)
CA (1) CA1212070A (de)
DD (1) DD202456A5 (de)
DE (1) DE3276073D1 (de)
DK (1) DK10982A (de)
FI (1) FI820064L (de)
GR (1) GR75833B (de)
IL (1) IL64705A0 (de)
MX (1) MX157087A (de)
NO (1) NO820074L (de)
PL (1) PL234880A1 (de)
PT (1) PT74271B (de)

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GB2118973A (en) * 1982-04-27 1983-11-09 Corrintec Uk Ltd Electrical connector and manufacture thereof
AU8083394A (en) * 1993-10-20 1995-05-08 Orbit Technologies, Inc. Coating for a resistance welding device
AT403674B (de) * 1995-11-08 1998-04-27 Euroligna Masch Aggregate Führungsschiene mit profilrohr und verfahren zu deren herstellung

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FR774077A (fr) * 1934-06-02 1934-11-30 Fortin & Saunier Ets Perfectionnement aux appareils portatifs pour dépôts électrolytiques
US3743590A (en) * 1971-04-26 1973-07-03 R Roll Electro plating device
US4206028A (en) * 1976-12-14 1980-06-03 Inoue-Japax Research Incorporated Electrochemical polishing system
JPS6056238B2 (ja) * 1979-06-01 1985-12-09 株式会社井上ジャパックス研究所 電気メツキ方法

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Title
Guy, Metall Runde für Ingenieure, Akad. Verlagsges. Ffm (1979) Bd 7 p. 354/355 *

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BR8200156A (pt) 1982-11-03
PL234880A1 (en) 1983-05-09
PT74271A (en) 1982-02-01
KR830009256A (ko) 1983-12-19
DK10982A (da) 1982-07-14
GR75833B (de) 1984-08-02
MX157087A (es) 1988-10-21
DE3276073D1 (en) 1987-05-21
CA1212070A (en) 1986-09-30
IL64705A0 (en) 1982-03-31
PT74271B (en) 1983-08-23
NO820074L (no) 1982-07-14
AU7944782A (en) 1982-07-22
EP0056331A1 (de) 1982-07-21
FI820064L (fi) 1982-07-14
DD202456A5 (de) 1983-09-14

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