EP0057505B1 - Verfahren und Vorrichtung zur Behandlung elektrisch leitender Materialien, dazu verwendete Lösungen und auf diese Weise erzeugte Produkte - Google Patents

Verfahren und Vorrichtung zur Behandlung elektrisch leitender Materialien, dazu verwendete Lösungen und auf diese Weise erzeugte Produkte Download PDF

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Publication number
EP0057505B1
EP0057505B1 EP82300139A EP82300139A EP0057505B1 EP 0057505 B1 EP0057505 B1 EP 0057505B1 EP 82300139 A EP82300139 A EP 82300139A EP 82300139 A EP82300139 A EP 82300139A EP 0057505 B1 EP0057505 B1 EP 0057505B1
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EP
European Patent Office
Prior art keywords
solution
matrix
sem
conductive element
fusion
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Expired
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EP82300139A
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English (en)
French (fr)
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EP0057505A3 (en
EP0057505A2 (de
Inventor
Joseph Ady
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Metafuse Ltd
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Metafuse Ltd
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Publication date
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Priority to AT82300139T priority Critical patent/ATE36014T1/de
Publication of EP0057505A2 publication Critical patent/EP0057505A2/de
Publication of EP0057505A3 publication Critical patent/EP0057505A3/en
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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
    • 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

Definitions

  • the present invention relates to fusion processes, apparatus for carrying out such processes and the products of such processes, and solutions for use in the process.
  • 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, vacuum 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, vacuum 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.
  • first conductive element shall refer to the matrix with which fusion is to be accomplished; and the term 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.
  • a process for the fusion at ambient temperature of about 20°C of at least one second conductive element comprising ferrous and non-ferrous metals or an alloy thereof, present in a dissociable form as part of a solution, into a matrix of a first conductive element comprising the steps of:
  • the invention provides a process for fusing a wide variety of conductive elements in either ferrous and non-ferrous matrices.
  • the process creates high bond strength without distortion or loss of work piece or matrix properties.
  • the process does not require gas-air operation and does not involve safety hazards.
  • the solution comprises .a process as claimed in Claim 1 characterized in that said solution comprises:
  • FIG. 1 illustrated, in general perspective view, an apparatus in accordance with the invention in which one output of an oscillator 11, powered by a power supply 10, is connected to an electrode 19 through an insulated handle 20.
  • the other output of oscillator 11 is connected, via line 16 and clamp 15, in the matrix or substrate 14 which is to be treated by the process of the invention.
  • the electrode is positively charged and the matrix is negatively charged when the signal is applied.
  • Electrode 19 is in the form of a plate incorporating a main channel 21 into which one side of the oscillator 11 output is led.
  • Channel 21 has a series of side channels 22 which open onto the undersurface of electrode 19.
  • 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 electrode 19 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. 3 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.
  • resistance 38 is varied; to vary the frequency inductance 33 is varied.
  • the travel speed may be determined by the following formula:
  • resistances R, and R 2 may be measured by any known means.
  • 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 11.
  • 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.
  • 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 to a more conventional metallic coating to avoid interference of such a coating with the elemental analysis.
  • the second conductive 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 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 Fig. 1 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 Fig. 6 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 Fig. 10.
  • the solution had the following characteristics: 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 VI The solution of Example VI was employed and applied to a steel matrix:
  • Fig. 17 shows a solid deposit of nickel of uniform density approximately 1.5 ⁇ m thick. As shown in the following Table and Fig. 18 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 solution had the following characteristics: The nickel concentration may vary form 2% to 10%, pH from 3.10 to 3.50; and resistivity from 17 ohms cm to 26 ohms cm.
  • Example VIII The same solution as was formulated for Example VIII 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 um.
  • 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.
  • 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 Fig. 22.
  • 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 Fig. 24.
  • aqueous solution of the following formulation was prepared: This solution had the following characteristics: 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 Fig. 26.
  • An SEM/EPMA scan across the interface indicated fusion of chromium to a depth of at least 5.0 11 m as shown on the table below and Fig. 28.
  • 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.
  • 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 Fig. 30.
  • 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 Fig. 32.
  • aqueous solution of the following formulation was prepared: This solution had the following characteristics: 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
  • aqueous solution of the following formulation was prepared: This solution had the following characteristics: 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.
  • An SEM/EPMA scan across the interface indicated fusion of cadmium to a depth of at least 4 11 m as shown on the Table below and Fig. 36.
  • aqueous solution of the following formulation was prepared: This solution had the following characteristics: 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 Fig. 38.
  • aqueous solution of the following formulation was prepared: This solution had the following characteristics: 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 Fig. 40.
  • aqueous solution of the following formulation was prepared: This solution had the following characteristics: 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.
  • aqueous solution of the following formulation was prepared: This solution had the following characteristics: 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 Fig. 46.
  • aqueous solution of the following formulation was prepared: This solution had the following characteristics: 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 11m as shown on the Table below and Fig. 48.
  • 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 behaviour.
  • 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 bull 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)
  • Electroplating Methods And Accessories (AREA)
  • Chemically Coating (AREA)
  • Electroplating And Plating Baths Therefor (AREA)

Claims (4)

1. Verfahren zur Verbindung von zumindest einem zweiten leitenden Element, das Eisen und Nichteisenmetalle oder eine daraus bestehende Legierung enthält und in dissozierbarer Form als Teil einer Lösung vorliegt, in einer Matrix eines ersten leitenden Elementes bei einer Umgebungstemperatur von etwa 20°C, bestehend aus folgenden Schritten:
a) in Kontakt bringen der Lösung, die einen spezifischen Widerstand zwischen 5 und 500 Ohm cm aufweist, mit einem ausgewählten begrenzten Bereich der angrenzenden Oberfläche des ersten leitenden Elementes, das Eisen und Nichteisenmetalle oder eine daraus bestehende Legierung enthält.
b) die Anlegung eines unterbrochenen elektrisch pulsierenden Halbwellensignals zwischen 2,5 Microsekunden und 28,6 Nanosekunden mit einer Frequenz zwischen 400 Hz und 35 MHz an die Lösung und das erste leitende Element, wobei das angelegte Signal eine Amplitude von 3 Ampere pro 0,3 mm2 aufweist, wodurch das zweite leitende Element sich mit dem ersten leitenden Element im ausgewählten Bereich ohne wesentliche Wärmeerzeugung in einer Tiefe von mehr als 0,5 um Dicke verbindet.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Lösung 0,10 bis 10 Gewichtsprozent eines ersten Bestandteiles, das das zweite Metall in dissozierbarer Form enthält,
zumindest ein stabilisierendes, komplexbildendes Agens, das den ersten Bestandteil in Lösung hält, einen organischen Katalysator zur Beschleunigung der Reaktionsgeschwindigkeit und
ein Lösungsmittel aus der Gruppe enthält, die Wasser, ein organisches Lösungsmittel oder eine Mischung daraus umfaßt.
3. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß die wässrige Lösung einen pH-Wert zwischen 0,4 und 14 aufweist.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß das zweite leitende Element aus der Elementengruppe, 1b, 2b, 3b und 4b ausgewählt ist und daß das erste Element aus der Gruppe ausgewählt ist, die Eisen oder Nichteisenmetalle oder eine Legierung daraus umfaßt.
EP82300139A 1981-01-13 1982-01-12 Verfahren und Vorrichtung zur Behandlung elektrisch leitender Materialien, dazu verwendete Lösungen und auf diese Weise erzeugte Produkte Expired EP0057505B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT82300139T ATE36014T1 (de) 1981-01-13 1982-01-12 Verfahren und vorrichtung zur behandlung elektrisch leitender materialien, dazu verwendete loesungen und auf diese weise erzeugte produkte.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US22476281A 1981-01-13 1981-01-13
US31967281A 1981-11-09 1981-11-09
US224762 1994-04-08
US319672 1994-10-12

Publications (3)

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EP0057505A2 EP0057505A2 (de) 1982-08-11
EP0057505A3 EP0057505A3 (en) 1982-09-22
EP0057505B1 true EP0057505B1 (de) 1988-07-27

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EP82300139A Expired EP0057505B1 (de) 1981-01-13 1982-01-12 Verfahren und Vorrichtung zur Behandlung elektrisch leitender Materialien, dazu verwendete Lösungen und auf diese Weise erzeugte Produkte

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EP (1) EP0057505B1 (de)
KR (1) KR830009257A (de)
AU (1) AU7944882A (de)
BR (1) BR8200154A (de)
CA (1) CA1187035A (de)
DD (1) DD202312A5 (de)
DE (1) DE3278814D1 (de)
DK (1) DK11082A (de)
FI (1) FI820063L (de)
GR (1) GR75834B (de)
IL (1) IL64706A0 (de)
NO (1) NO820075L (de)
PL (1) PL234879A1 (de)
PT (1) PT74270B (de)

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
A. GUY: Metallkunde für Ingenieure, Akad. Verlagsgem. Ffm. (1970), p.355 *

Also Published As

Publication number Publication date
PL234879A1 (en) 1983-05-09
CA1187035A (en) 1985-05-14
EP0057505A3 (en) 1982-09-22
AU7944882A (en) 1982-07-22
FI820063L (fi) 1982-07-14
NO820075L (no) 1982-07-14
EP0057505A2 (de) 1982-08-11
BR8200154A (pt) 1982-11-03
PT74270B (en) 1986-01-10
PT74270A (en) 1982-02-01
IL64706A0 (en) 1982-03-31
KR830009257A (ko) 1983-12-19
GR75834B (de) 1984-08-02
DD202312A5 (de) 1983-09-07
DE3278814D1 (en) 1988-09-01
DK11082A (da) 1982-07-14

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